|Publication number||US6161555 A|
|Application number||US 09/230,940|
|Publication date||19 Dec 2000|
|Filing date||30 Sep 1997|
|Priority date||19 Apr 1994|
|Publication number||09230940, 230940, PCT/1997/17534, PCT/US/1997/017534, PCT/US/1997/17534, PCT/US/97/017534, PCT/US/97/17534, PCT/US1997/017534, PCT/US1997/17534, PCT/US1997017534, PCT/US199717534, PCT/US97/017534, PCT/US97/17534, PCT/US97017534, PCT/US9717534, US 6161555 A, US 6161555A, US-A-6161555, US6161555 A, US6161555A|
|Inventors||John Young-Fu Chen|
|Original Assignee||Applied Elastomerics, Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (96), Non-Patent Citations (42), Referenced by (69), Classifications (23), Legal Events (5)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This application is a continuation-in-part application of copending application No. 08/719,817 filed Sep. 30, 1996, which is a CIP of Ser. No. 08/665,343 filed Jun. 17, 1996 and a CIP of Ser. No. 08/612,586 filed Mar. 8, 1996 and a CIP of No. 08/581,125 filed Dec. 29, 1995, (now Pat. No. 5,962,572) and also a CIP of No. 08/581,191 filed Dec. 29, 1995, now U.S. Pat. No. 5,760,117 issued Jun. 2, 1998. This application is also a CIP of Ser. No. 08/581,188 filed Dec. 29, 1995, now abandoned and a CIP of Ser. No. 08/288,690 filed Aug. 11, 1994, now U.S. Pat. No. 5,633,286 and also a CIP of PCT/US94/07314 filed Jun. 27, 1994, and a CIP of PCT/US94/04278, filed Apr. 19, 1994. The subject matter contained in the related application is specifically incorporated herein by reference.
The present invention relates to dental floss and gum massager.
Thermoplastic elastomer SEBS gels are described in Pat. Nos. 5,334,646, 5,508,334, 5,262,468, 5,153,254, 4,618,213; and 4,369,284. These gels can be use for flossing because of their extreme softness and strength. The SEBS and SEPS triblock copolymer oil gels, however, do not have sufficient resistance to tearing when the gel is repeatedly notched or nicked by inserting and re-inserting between the teeth gaps while at the same time applying constant tension to the floss. This failure makes triblock copolymer gels much less desirable and commercially useless and unacceptable to the flossing consumer.
1. Statement Of The Invention
I have discovered an improved dental floss and gum massager made from novel compositions comprising gels with improved high tear strength, improved high tensile strength, and improved resistance to high stress rupture. The improved gels can be formed into gel strands, gel tapes, and gel sheets for massaging the gum and flossing the teeth. The gel floss can be in the form of strands and tapes when rapped around the fingers for holding, extending, and flossing are advantageously more comfortable and less restricting to blood circulation in the fingers than conventional dental floss. When the gel floss is in the form of a sheet, it is additionally advantages for the sheet to have at least two separate selective sized holes at a selective distance apart for holding said sheet by one or more fingers of one or both hands, said sheet having a selected shaped peripheral sheet edge of a selective thickness, said holes being a selective distance from said edge and sized for insertion through by at least one said finger of each hand for holding said sheet and gripping, pulling, pushing, deforming, working, deforming, manipulating, folding and guilding said sheet edge for massaging the gum and flossing the teeth without substantial constriction of blood flow of said fingers by said sheet.
I have now discovered gels with improved damage tolerance, crack propagation resistance and tear resistance which are advantageously suitable for use as dental floss that are from about twice to about ten times or better in lowering the gap insertion breaking frequency than same rigidity gels made from triblock copolymer oil gels alone.
The invention comprises gels and articles useful as floss made from mixtures of triblock copolymers having at least one different midblock or multiblock copolymers having one, two or more different midblocks which gels exhibit advantages of improved tensile strength, improved tear strength (propagation resistance under tension and continuous notching and nicking) and additionally improved resistance to high stress rupture. Such combination of properties are not found in gels of substantially the same rigidity made from SEBS or SEPS triblock copolymers alone. The gels of the present invention exhibit low set, high dimensional stability, crack, tear, craze, and creep resistance under tension, excellent tensile strength and high elongation, long service life under shear, stress and strain and capable of withstanding repeated dynamic shear, tear and stress forces, excellent processing ability for cast molding, extruding, fiber forming film forming and spinning, non-toxic, nearly tasteless and odorless, soft and strong, optically clear, highly flexible, possessing elastic memory, substantially with little or no plasticizer bleedout. The gels are especially advantageously suitable where resistance to crazing, cracking, fracturing, and catastrophic failure while under dynamic stretch tension loads in an environment where continuous or repeated shearing, cutting, nicking, notching, lacerating, mutilating, and tearing of the gel in contact with or between other bodies (i.e., abraded by repeated contact with another body or bodies) are encountered, such as those forces acting during dental flossing. The resistance to tear propagation or ability to stop direct crack propagation under dynamic tension loads is a critical factor and an advantage of the present gels over triblock copolymer gels alone.
Still further, the tear resistance of gels floss based on typical SEBS or SEPS triblock copolymers can be improved with the addition of the multiblock copolymers or selected crystalline block copolymers forming the gels of the invention.
Generally, the instant improved gels comprises: (I) 100 parts by weight of one or more high viscosity or selected low viscosity linear, branched, radial, star-shaped, multi-arm or branched block copolymers or mixtures of two or more such block copolymers, said block copolymers having one or more midblocks, said midblocks comprising one or more substantially amorphous midblocks or one or more substantially crystalline polyethylene midblocks and with nil, one or more amorphous midblocks with the proviso that when said gel comprises a mixture of one or more of a substantially amorphous midblock block copolymers, at least one selected substantially crystalline polyethylene midblock block copolymer is present in combination in said admixture; optionally in combination with a selected amount of one or more of a (II) polymer or copolymer, and selected amounts of a plasticizing oil (III) sufficient to achieve gel rigidities of from less than about 2 gram Bloom to about 1,800 gram Bloom with the proviso that said block copolymers having nil amorphous midblocks are combined with at least one block copolymer having at least one amorphous midblock.
As used herein, the term "gel rigidity" in gram Bloom is determined by the gram weight required to depress a gel a distance of 4 mm with a piston having a cross-sectional area of 1 square centimeter at 23° C.
The gels comprising thermoplastic elastomer block copolymers having one or more advantageously sufficient amount of crystalline polyethylene midblocks of the invention are hereafter referred to as "elastic-crystalline gels" or simpler "crystal gels". The block midblocks of copolymers forming the crystal gels of the invention are characterized by sufficient crystallinity as to exhibit a melting endotherm of at least about 40° C. as determined by DSC curve.
The various types of high viscosity or low viscosity linear, branched, radial, star-shaped or multiarm block copolymers or mixtures of two or more such block copolymers employed in forming the crystal gels of the invention are of the general configurations A-Z-A and (A-Z)n, wherein the subscript n is two or more. In the case of multiarm block copolymers where n is 2, the block copolymer denoted by (A-Z)n is A-Z-A. It is understood that the coupling agent is ignored for sake of simplicity in the description of the (A-Z)n block copolymers.
The end block segment (A) comprises a glassy amorphous polymer end block segment, preferably, polystyrene. The midblocks (Z) comprises one or more midblocks of substantially poly(butylene) or -B- as further denoted below and substantially crystalline poly(ethylene) (simply denoted by "-E- or (E)") with or without one or more amorphous midblocks of poly(butylene), poly(ethylene-butylene), poly(ethylene-propylene) or combination thereof (the amorphous midblocks are denoted by "-B- or (B)", "-EB- or (EB)", and "-EP- or (EP)" respectively or simply denoted by "-W- or (W)" when referring to one or more of the amorphous midblocks as a group) The A and Z portions are incompatible and form a two or more-phase system consisting of sub-micron amorphous glassy domains (A) interconnected by (Z) chains. The glassy domains serve to crosslink and reinforce the structure. This physical elastomeric network structure is reversible, and heating the polymer above the softening point of the glassy domains temporarily disrupt the structure, which can be restored by lowering the temperature.
The (I) linear, branched, radial, star-shaped, multi-arm or branched block copolymers block copolymers are characterized as having a Brookfield Viscosity value at 5 weight percent solids solution in toluene at 30° C. of from less than about 40 cps to about 60 cps and higher, advantageously from about 40 cps to about 160 cps and higher, more advantageously from about 50 cps to about 180 cps and higher, still more advantageously from about 70 cps to about 210 cps and higher, and even more advantageously from about 90 cps to about 380 cps and higher.
The (I) linear, branched, radial, star-shaped, multi-arm or branched block copolymers are characterized as having a Brookfield Viscosity value at 5 weight percent solids solution in toluene at 30° C. of from about 80 cps to about 380 cps and higher, advantageously from about 150 cps to about 260 cps and higher, more advantageously from about 200 cps to about 580 cps and higher, and still more advantageously from about 100 cps to about 800 cps and higher.
The substantially amorphous block copolymers (SEBS or (SEB)n with high butylene content and SEPS or (SEP)n with high isopropylethyene content) forming components of mixtures of the gels of the present invention are of high molecular weights, but by their nature exhibit lower viscosity which advantageously range from less than about 1,000 cp to about 100 cp toluene viscosity at 10% solids at 25° C., more advantageously less than about 500 cp to about 100 cp, still more advantageously less than about 200 cp to about 90 cp or less.
The crystal gels can be made in combination with a selected amount of one or more selected polymers and copolymers (II) including thermoplastic crystalline polyurethane elastomers with hydrocarbon midblocks, homopolymers, copolymers, block copolymers, polyethylene copolymers, polypropylene copolymers, and the like described below.
The crystal gels forming the floss of the invention are also suitable in physically interlocking or forming with other selected materials to form gel composites combinations. The materials are selected from the group consisting of foam, plastic, fabric, various natural and synthetic resins particles, fibers and films.
Commercial resins which can aid in adhesion to materials (plastics, glass, and metals) may be added in minor amounts to the gelatinous elastomer composition, these resins include: polymerized mixed olefins (Super Sta-tac, Betaprene Nevtac, Escorez, Hercotac, Wingtack, Piccotac), polyterpene (Zonarez, Nirez, Piccolyte, Sylvatac), glycerol ester of rosin (Foral), pentaerythritol ester of rosin (Pentalyn), saturated alicyclic hydrocarbon (Arkon P), coumarone indene (Cumar LX), hydrocarbon (Picco 6000, Regalrez), mixed olefin (Wingtack), alkylated aromatic hydrocarbon (Nevchem), Polyalphamethylstyrene/vinyl toluene copolymer (Piccotex), polystyrene (Kristalex, Piccolastic), special resin (LX-1035), and the like.
Furthermore, the interlocking materials with the gel of the invention may be made from flexible materials, such as fibers and fabrics of cotton, flax, and silk. Other flexible materials include: elastomers, fiber-reinforced composites, mohair, and wool. Useful synthetic fibers include: acetate, acrylic, aremid, glass, modacrylic polyethylene, nylon, olefin, polyester, rayon, spandex, carbon, sufar, polybenzimidazole, and combinations of the above. Useful open-cell plastics include: polyamides, polyimides, polyesters, polyisocyanurates, polyisocyanates, polyurethanes, poly(vinyl alcohol), etc. Open-celled Plastic (foams) suitable for use with the compositions of the invention are described in "Expanded Plastics and Related Products", Chemical Technology Review No. 221, Noyes Data Corp., 1983, and "Applied Polymer Science", Organic Coatings and Plastic Chemistry, 1975. These publications are incorporated herein by reference. These include: open and non-opened cell silicone, polyurethane, polyethylene, neoprene, polyvinyl chloride, polyimide, metal, ceramic, polyether, polyester, polystyrene, polypropylene. Example of such foams are: Thanol®, Arcol®, Ugipol®, Arcel®, Arpak®, Arpro®, Arsan®, Dylite®, Dytherm®, Styrofoam®, Trymer®, Dow Ethafoam®, Ensolite®, Scotfoam®, Pyrell®, Volana®, Trocellen®, Minicel®, and the like.
The various aspects and advantages of the invention will become apparent to those skilled in the art upon consideration of the accompanying disclosure and the drawings.
FIG. 1. Representative sectional views of unexpanded gel floss of the invention.
FIG. 2. Representative views of expanded gel floss of the invention.
FIG. 3. Representative views of expanded gel floss of the invention.
FIG. 4. Representative sectional views of various gel floss of the invention.
The process of flossing involve inserting a segment of the floss into each gap between the teeth, moving the floss with a up-and-down motion while holding it tightly in tension and rubbing the sides of each tooth down to the gum line to remove plaque. The main problem with conventional dental floss, such as waxed, unwaxed nylon, spongy nylon, and teflon is that when tension is applied while inserting it between the teeth, the floss can forcefully strike the gum or gum line as it is inserted through a tight teeth gap suddenly releasing with a snap, impacting the gum, producing pain, at times causing lacerations or bleeding of the gums. Another serious problem using conventional floss is that the tension applied in flossing is transferred to the floss windings around the fingers as the floss is pulled tightly in tension for insertion through the gap and in tension for up-and-down flossing. With the flossing of each teeth, the cumulative tensions cause the windings to become ever tighter. As with teflon floss, more windings are needed to maintain tension because of natural slippage. Without loosening of the windings, eventually, the fingers can become extremely uncomfortable turning blue from lack of circulation. With the use of conventional floss and teflon less so, shredding of the floss caused by tight teeth gaps is another problem. Up to now, the process of flossing can be an uncomfortable experience. People knowing they should floss do not or do not do so as often because of the pain and discomfort involved. Most dentist would not recommend young children to floss their own teeth because serious gum damage may result due to improper flossing.
Tearing of the SEES gels has been of major concern. In general, amorphous gels such as those made form SEES and SEPS can fail catastrophically when subjected repeatedly to applied forces of high dynamic and static deformations, such as extreme compression, torsion, high tension, high elongation involving tearing and high stress rupture conditions encountered during flossing. Additionally, the development of cracks or crazes resulting from a large number of deformation cycles can induce catastrophic fatigue failure of amorphous gel composites, such as tears and rips between the surfaces of the amorphous gel and substrates or at the interfaces of interlocking material(s) and gel. Consequently, such amorphous gels are inadequate for the most demanding applications involving endurance at high stress and strain levels over an extended period of time. Consequently, when the gel is used as floss which when cut or notched during use, the resulting catastrophic failure renders the gel floss useless. Therefore, the World needs a softer, gentler, more gum friendly non-lacerating dental floss.
Normally, for triblock copolymer gel floss, tensile stress, bending, or twisting are not the cause of failure; it is the crack openings, v-notches or nicks formed on opposite sides of the gel floss as it is inserted and re-inserted into the teeth gap under continuous tension that develops and fails catastrophically. It is observed that triblock copolymer gel floss break apart suddenly under tension during the first insertion, often times it can catastrophically break apart during the second or third insertion, and more often times it can catastrophically snap apart during the third or fourth insertions. In most instances, the triblock copolymer gel floss fail by the fourth or fifth insertions when inserted in a normal tight gap between normal front teeth and fail on the first or second insertions when used between facing tight contacting amalgam molars.
The reason why this happens is possibly that at the point where the gel floss is damaged (cut, notched or nicked) a craze front develops as more voids form along the line perpendicular to the floss' elongated direction (i.e., applied tension) resulting in sudden unstoppable fracturing of the bulk material ahead of the notched point causing complete catastrophic failure of the floss.
Consequentially, its very frustrating to attempt to floss a full set of upper or lower teeth with triblock copolymer gel floss. It is the complete, unstoppable catastrophic failure of the triblock copolymer gel floss in tension while being worked in the gap of the teeth that must be prevented in order for the gel to be useful for flossing.
Therefore, gels providing greater tear resistance under applied tension are needed before "gels" as a class of materials can be commercialized for use as dental floss. The gap insertion "breaking frequency" of the gel floss must be substantially lowered before the gel can be acceptable by the consumer for flossing. Breaking frequency means the number of flossing cycles to break of a floss where one cycle comprises an insertion and extraction a floss between the teeth gap.
Block copolymers with polyethylene midblocks alone do not form suitable gels for use in making the gels of the invention. Crystalline midblock regions needs to be balanced with amorphous midblock regions in order to obtain soft, flexible and elastic gels with the desired crystalline properties that are not found in typical SEBS and SEPS gels.
The polymers forming the gels of the invention comprises crystalline/glassy domain/amorphous structures which are described and illustrate in copending application No. 863,794. Although the structure can be spheroid, cylinders and plates are also within the scope of the present invention. Cylinder and plate structure are obtained with increasing glassy A end blocks. From about 15-30% by weight of A blocks, the block copolymer structure is spheroid. From about 33 about 40% by weight of A blocks, the block copolymer structure becomes cylindrical; and above about 45% A blocks, the structure becomes less cylindrical and more plate like.
In order to obtain elastic crystal gels forming the floss of the invention, it is necessary that the selective synthesis of butadiene produce sufficient amounts of 1,4 poly(butadiene) that on hydrogenation can exhibit "crystallinity" in the midblocks. In order for the block copolymers forming the crystal gels of the invention to exhibit crystallinity, the crystalline midblock segments must contain long runs of --CH2 -- groups. There should be approximately at least 16 units of --(CH2)-- in sequence for crystallinity. Only the (--CH2 --)4 units can crystallize, and then only if there are at least 4 units of (--CH2 --)4 in sequence; alternatively, the polyethylene units are denoted by [--(CH2 --CH2 --CH2 --CH2)--]4, [(--CH2 --)4 ]4 or (--CH2 --)16. The amount of (--CH2--)16 units forming the (E) midblocks of the block copolymers comprising the crystal gels of the invention should be at least about 20% which amount is capable of exhibiting a melting endotherm in differential scanning calorimeter (DCS) curves.
Advantageously, the elastomer midblock segment should have a crystallinity of at least about 20% of (--CH2 --)16 units of the total mole % forming the midblocks of the block copolymer, more advantageously at least about 25%, still more advantageously at least about 30%, especially advantageously at least about 40% and especially more advantageously at least about 50% and higher. Broadly, the crystallinity of the midblocks should range from at least about 20% to about 60%, less broadly from at least about 18% to about 65%, and still less broadly from at least 22% to about 70%.
The melting endotherm in DSC curves of the crystalline block copolymers comprising at least 20% crystallinity are much higher than conventional amorphous block copolymers. The maximum in the endotherm curves of the crystalline block copolymers occurs at about 40° C., but can range from greater than about 25° C. to about 60° C. and higher. The crystalline block copolymers forming the crystal gels of the invention can exhibit melting endotherms (as shown by DSC) of about 25° C. to about 75° C. and higher. More specific melting endotherm values of the crystalline midblock block copolymers include: about 28° C., 29° C., 30° C., 31° C., 32° C., 33° C., 34° C., 35° C., 36° C., 37° C., 38° C., 39° C., 40° C., 41° C., 42° C., 43° C., 44° C., 45° C., 46° C., 47° C., 48° C., 49° C., 50° C., 51° C., 52° C., 53° C., 54° C., 55° C., 56° C., 57° C., 58° C., 59° C., 60° C., 61° C., 62° C., 63° C., 64° C., 65° C., 66° C., 67° C., 68° C., 69° C., 70° C., 71° C., 72° C., 73° C., 74° C., 75° C., 76° C., 77° C., 78° C., 79° C., 80° C., 90° C., 110° C., 120° C., and higher, whereas, the melting endotherm (DSC) for conventional amorphous midblock segment block copolymers are about 10° C. and lower.
The melting endotherm is seen on heating and a sharp crystallization exotherm is seen on cooling. Such midblock crystallization endothermic and exothermic characteristics are missing from DSC curves of amorphous gels. The crystallization exotherm and fusion endortherm of the crystalline block copolymer gels of the invention are determined by ASTM D 3417 method.
Generally, the method of obtaining long runs of crystalline --(CH2)-- is by sequential block copolymer synthesis followed by hydrogenation. The attainment of crystal gels of the instant invention is solely due to the selective polymerization of the butadiene monomer (forming the midblocks) resulting in one or more predetermined amount of 1,4 poly(butadiene) blocks followed by sequential polymerization of additional midblocks and hydrogenation to produce one or more crystalline midblocks of the final block copolymers.
The crystalline block copolymers are made by sequential block copolymer synthesis, the percentage of crystallinity or (--CH2 --)16 units should be at least about (0.67)4 or about 20% and actual crystallinity of about 12%. For example, a selectively synthesized S-EBn -S copolymer having a ratio of 33:67 of 1,2 and 1,4 poly(butadiene) on hydrogenation will result in a midblock with a crystallinity of (0.67)4 or 20%. For sake of simplicity, when n is a subscript of -EB-, n denotes the percentage of (--CH2--)4 units, eg, n=67 or 20% crystallinity which is the percentage of (0.67)4 or "(--CH2 --)16 " units. Thus, when n=28 or 72% of (--CH2 --)4 units, the % crystallinity is (0.72)4 or 26.87% crystallinity attributed to (--CH2 --)16 units, denoted by -EB28 -. As a matter of convention, and for purposes of this specification involving hydrogenated polybutadiene: the notation -E- denotes at least about 85% of (--CH2 --)4 units. The notation -B- denotes at least about 70% of [--CH2 --CH(C2 H5)--] units. The notation -EB- denotes between about 15 and 70% [--CH2 --CH(C2 H5)--] units. The notation -EBn -- denotes n % [--CH2 --CH(C2 H5)--] units. For hydrogenated polyisoprene: The notation -EP- denotes about at least 90% [--CH2 --CH(CH3)--CH2 CH2 --] units. The notation -P- denotes about at least greater than about 70% polyisopropylethyene units.
Likewise, in order to obtain the highly amorphous midblock components such as -B- forming the elastic gels of the floss of the invention, it is necessary that the selective synthesis of butadiene produce sufficient amounts of vinyl or 1,2 poly(butadiene) that on hydrogenation can exhibit "substantially amorphous polybutene" midblocks. The notation -B- denotes greater than above about 70% [--CH2 --CH(C2 H5)--]n polybutene units and -P- denotes greater than about 70% [--CH(CH--2CH3)--CH2 --]n polyisopropylethyene units. The substantially amorphous midblocks -EBn - and -EPn - of SEBn S and SEPn S (or more simply denoted when n % is greater than about 70% as -B- and -P-) are more advantageously when n % is greater than about 75%, still more advantageously greater than about 80%, and still more advantageously greater than about 85%, and even still more advantageously greater than about 90% or higher. Typically, high polybutene content SEBn S or simply SBS is made by adding structure modifiers, such as ethers, which gives more 1,2 polybutadiene and after hydrogenation, more polybutene, resulting in less crystallinity, softer block copolymer, lower viscosity, and higher Tg. Likewise, high polyisopropylethyene content SEPn S or simply S-P-S is made by adding structure modifiers to give more 3,4 structure and after hydrogenation, more polyisopropylethyene, resulting in softer block copolymer, lower viscosity, and higher Tg.
The major advantages of SEBn S and SEPn S over SEBS, SEPS (when n % greater=than about 70%) is the Tg of poly(styrene-ethylene-butylene>70 -styrene) and poly(styrene-ethylene/propylene-isopropylethyene>70 -styrene) are much higher; the gel rigidities are lower; and the viscosities are much lower. More specifically, the Tg of SEBS is typically about -58° C. and the Tg of SEPS is typically about -50° to about -60° C. Whereas, the Tg of SEBn S and SEPn S with high butylene content and high isopropylethyene content can be advantageously much higher of about less than about -40° C., advantageously -30° C. and more advantageously higher of about -27° C. and higher.
It is extraordinary that where typical SEBS and SEPS gels fails to provide adequate tensile strength, fails to provide adequate tear strength, and fails to provide adequate resistance to high stress rupture suitable for use as dental floss, hereto unknown and unappreciated modification of the midblock structures provide heretofore unrealizable improved higher tensile strength, improved higher tear strength, and improved higher resistance to high stress rupture.
Theory notwithstanding, SEBS and SEPS gels fail to provide adequate properties for use as dental floss. The following is known:
i) gels made from typical SEBS which is created from a mixture of 1, 4- and 1,2-polybutadiene to provide a random mixture of ethylene and butylene units adequate to suppress crystallinity (as noted by Legge). Such gels can not provide adequate tear strength and lack adequate resistance to high stress rupture.
ii) gels made from typical SEPS which is created by hydrogenation of cis-1,4-polyisoprene results in a 1:1 ethylene/propylene elastomer midblock (as noted by Legge). Such gels can not provide adequate tear strength and lack adequate resistance to high stress rupture.
Contrary to the inferior properties of the above gels 1) and 2), the following gels are found to be superior and of improved high tear strength, improved resistance to high stress rupture and sufficient adequate tensile strength for use as dental floss:
iii) gels made from an admixture of a high crystalline ethylene content S-En B-S block copolymer and a high butylene content S-EBn -S block copolymer.
iv) gels made from an admixture of a high crystalline ethylene content S-En B-S block copolymer and a high polyisopropylethyene content S-EPn -S block copolymer.
v) gels made from an admixture of a high crystalline ethylene content S-En B-S block copolymer, a high butylene content S-EBn -S block copolymer, and a high polyisopropylethyene content S-EPn -S block copolymer
vi) S-E-EB>70 -E-S gels made by coupling S-E-EB>70.
vii) S-E-EP>70 -E-S gels made by coupling S-E-EP>70.
viii) gels made from linear, branched, radial, star-shaped, multi-arm or branched block copolymers having sufficient multiple midblock components of high crystalline ethylene content, high butylene content, and/or high isopropylethyene content including all combinations and permutations and mixtures of such block copolymers and as further described below.
Generally, one or more (E) midblocks can be incorporated at various positions along the midblocks of the block copolymer's. Using the sequential process for block copolymer synthesis, The (E) midblocks can be positioned as follows:
iv) and etc.
The highly amorphous or highly crystalline midblock components:
The lower flexibility of block copolymer crystal gels due to (E) midblocks can be balanced by the addition of sequentially (W) midblocks. For example, the sequentially synthesized block copolymer S-E-EB-S can maintain a high degree of flexibility due to the presence of amorphous -EB- block. The sequential block copolymer S-E-EB-B-S can maintain a high degree of flexibility due to the presence of amorphous -EB- and -B- midblocks. The sequential block copolymer S-E-EP-E-S can maintain a high degree of flexibility due to the presence of -EP- midblock. The sequential block copolymer S-E-B-S can maintain a high degree of flexibility due to the presence of the -B-, butylene midblock. For S-E-S, where the midblock is substantially crystalline and flexibility low, physical blending with amorphous block copolymers such as S-EB-S, S-B-S, S-EP-S, S-EB-EP-S, (S-EP)n and the like can produce more softer, less rigid, and more flexible crystal gel.
In additional to the block copolymers S-E-EB-S and S-E-EP-S, S-E-EB-E-S can be made by coupling S-E-EB and S-E-EP-E-S can be made by coupling S-E-EP or by making it sequentially. Multi-arm of such block copolymer can also be made.
Because of the (E) midblocks, the crystal gels forming the floss of the invention exhibit different physical characteristics and improvements over substantially amorphous gels including damage tolerance, improved crack propagation resistance, improved tear resistance producing knotty tears as opposed to smooth tears, crystalline melting point of at least 28° C., improved resistance to fatigue, higher hysteresis, etc. Moreover, the crystal gels forming the floss when stretched exhibit additional yielding as shown by necking caused by stress induced crystallinity.
Regarding resistance to fatigue, fatigue (as used herein) is the decay of mechanical properties after repeated application of stress and strain. Fatigue tests give information about the ability of a material to resist the development of cracks or crazes resulting from a large number of deformation cycles. Fatigue test can be conducted by subjecting samples of amorphous and crystal gels to deformation cycles to failure (appearance of cracks, crazes, rips or tears in the gels).
Tensile strength can be determined by extending a selected gel sample to break as measured at 180° U bend around a 5.0 mm mandrel attached to a spring scale. Likewise, tear strength of a notched sample can be determined by propagating a tear as measured at 180° U bend around a 5.0 mm diameter mandrel attached to a spring scale.
Various block copolymers can be obtained which are amorphous, highly rubbery, and exhibiting minimum dynamic hysteresis:
The monomer butadiene can be polymerized in a ether/hydrocarbon solvent to give a 50/50 ratio of 1,2 poly(butadiene)/1,4 poly(butadiene) and on hydrogenation no long runs of --CH2 -- groups and negligible crystallinity, ie, about (0.5)4 or 0.06 or 6% and actual crystallinity of about 3%. Due to the constraints of Tg and minimum hysteresis, conventional S-EB-S have ethylene-butylene ratios of about 60:40 with a crystallinity of about (0.6)4 or 0.129 or 12% and actual crystallinity of about 7.7%.
The monomer isoprene when polymerized will produce 95% 1,4 poly(isoprene)/5% 3,4 polycisoprene) and upon hydrogenation will form amorphous, rubbery poly(ethylene-propylene) midblock and no long runs of --CH2 -- and no crystallinity.
The polymerization of a 50/50 mixture of isoprene/butadiene monomers in suitable ether/hydrocarbon solvents to give equal amounts of 1,2 and 1,4 poly(butadiene) on hydrogenation will produce a maximum crystallinity of (0.25)4 or 0.4%. The actual crystallinity would be approximately about 0.2%, which is negligible and results in a good rubbery midblock.
The polymerization of a 80/20 mixture of isoprene/butadiene monomers in suitable ether/hydrocarbon solvents to give equal amounts of 1,2 and 1,4 poly(butadiene) will upon hydrogenation produce a low crystallinity of (0.10)4 or 0.01%. The actual crystallinity would be approximately about 0.006%, which is negligible and results in a good rubbery midblock.
The polymerization of a 20/80 mixture of isoprene/butadiene monomers in suitable ether/hydrocarbon solvents to give equal amounts of 1,2 and 1,4 poly(butadiene) will upon hydrogenation produce a low crystallinity of (0.4)4 or 2.56%. The actual crystallinity would be approximately about 1.53%, which is negligible and results in a good rubbery midblock.
The polymerization of a 20/80 mixture of isoprene/butadiene monomers in suitable ether/hydrocarbon solvents to give a 40:60 ratio of 1,2 and 1,4 poly(butadiene) will upon hydrogenation produce a low crystallinity of (0.48)4 or 5.3%. The actual crystallinity would be approximately about 3.2%, which is negligible and results in a good rubbery midblock.
The midblocks (Z) of one or more -E-, -B-, -EB-, or -EP- can comprise various combinations of midblocks between the selected end blocks (A); these include: -E-EB-, -E-EP-, -B-EP-, -B-EB-, -E-EP-E-, -E-EB-B-, -B-EP-B-, -B-EB-B-, -E-B-EB-, -E-B-EP-, -EB-EP-, -E-EB-EP-, -E-EP-EB-, -B-EB-EP-, -B-EP-EB-, -E-EP-E-EP-, -E-EP-E-EB-, -B-EP-B-EP-, -B-EB-B-EB-, -B-EB-B-EP-, -E-EB-B-EP-, -E-EP-B-EB- and the like.
The block copolymers of (A-Z-A) can be obtained by sequential synthesis methods followed by hydrogenation of the midblocks. As denoted above, abbreviations are interchangeably used, for example, (S-E-EP-S) denotes poly(styrene-ethylene-ethylene-co-propylene-styrene). Other linear block copolymers (denoted in abbreviations) include the following: (S-E-S), (S-E-EB-S), (S-E-EP-S), (S-B-EP-S), (S-B-EB-S), (S-E-EP-E-S), (S-E-EB-B-S), (S-B-EP-B-S), (S-B-EB-B-S), (S-E-B-EB-S), (S-E-B-EP-S), (S-EB-EP-S), (S-E-EB-EP-S), (S-E-EP-EB-S), (S-B-EB-EP-S), (S-B-EP-EB-S) and the like.
The multiblock star-shaped (or radial) copolymers (A-Z)n X can be obtained by sequential synthesis methods including hydrogenation of selected block copolymers made by polymerizing half of the block copolymers such as SBS or SIS and couple the halves with a coupling agent such as an organic dihalide; or couple with an agent such as SnC14, which results in star-shaped block copolymers (four branches). Coupling with divinyl benzene give block copolymers which are very highly branched. Radial block copolymers suitable for use in forming the crystal gels of the present invention include: (S-E)n, (S-E-EB)n, (S-E-EP)n, (S-B-EP)n, (S-B-EB)n (S-E-EP-E)n, (S-E-EB-B)n, (S-B-EP-B)n, (S-B-EB-B)n, (S-E-B-EB)n, (S-E-B-EP)n, (S-EB-EP)n, (S-E-EB-EP)n, (S-E-EP-EB)n, (S-B-EB-EP)n, (S-B-EP-EB)n, (S-E-EP-E-EP)n, (S-E-EP-E-EB)n, (S-EP-B-EP)n, (S-B-EB-B-EB)n, (S-B-EB-B-EP)n, (S-E-EB-B-EP)n and counter part multifunctional block copolymers:(R)n -E-S, (R)n -E-EB-S, (R)n -E-EP-S, (R)n -E-EP-E-S, (R)n -E-EB-B-S, (R)n -E-B-EB-S, (R)n -E-B-EP-S, (R)n -E-EB-EP-S, (R)n -E-EP-EB-S and the like. In the above notation, "-E-" denotes substantially crystalline polyethylene midblock.
The selected amount of crystallinity in the midblock should be sufficient to achieve improvements in one or more physical properties including improved damage tolerance, improved crack propagation resistance, improved tear resistance, improved resistance to fatigue of the bulk gel and resistance to catastrophic fatigue failure of crystal gel composites, such as between the surfaces of the crystal gel and substrate or at the interfaces of the interlocking materials) and crystal gel, which improvements are not found in amorphous gels at corresponding gel rigidities.
Selected (I) linear, branched, radial, star-shaped, multi-arm or branched block copolymers utilized in forming the crystal gels forming the floss of the invention are characterized as having an ethylene to butylene midblock ratio (E:B) of about 85:15 to about 65:35. Advantageously, the butylene concentration of the midblock is about 35% or less, more advantageously, about 30% or less, still more advantageously, about 25% or less, especially advantageously, about 20% or less. Advantageously, the ethylene to butylene midblock ratios can range from about 89:11, 88:12, 87:13, 86:14, 85:15, 84:16, 83:17, 82:18, 81:19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26, 73:27, 72:28, 71:29, 70:30, 69:31, 68:32, 67:33, 66:34 to about 65:35.
The A to Z midblock ratio of the block copolymers suitable for forming crystal gels of the invention can range from about 20:80 to 40:60 and higher. More specifically, the values can be 15:85, 19:81, 20:80, 21:79. 22:78. 23:77, 24:76, 25:75, 26:74, 27:73, 28:72, 29:71, 30:70, 31:69, 32:68, 33:67, 34:66, 35:65, 36:64, 37:63, 38:62, 39:61, 40:60, 41:59, 42:58, 43:57, 44:65, 45:55, 46:54, 47:53, 48:52, 49:51, 50:50, 51:49 and 52:48.
The crystal gels forming the floss can optionally comprise selected major or minor amounts of one or more polymers or copolymers (II) provided the amounts and combinations are selected without substantially decreasing the desired properties. The polymers and copolymers can be linear, star-shaped, radial, branched, or multiarm; these including: (SBS) styrene-butadiene-styrene block copolymers, (SIS) styrene-isoprene-styrene block copolymers, low and medium viscosity (S-EB-S) styrene-ethylene-butylene-styrene block copolymers, (S-EP) styrene-ethylene-propylene block copolymers, (S-EP-S) styrene-ethylene/propylene-styrene block copolymers, (S-EP-S-EP) styrene-ethylene/propylene-styrene-ethylene/propylene) block copolymers, (S-E-EPS) styrene-ethylene-ethylene/propylene-styrene block copolymers, (SB)n styrene-butadiene and (S-EB)n, (S-EB-S)n, (S-E-EP)n (SEP)n, (SI)n multi-arm, radial, branched or star-shaped copolymers, polyethyleneoxide (EO), poly(dimethylphenylene oxide), teflon (TFE, PTFE, PEA, FEP, etc), optical clear amorphous copolymers based on 2,2-bistrifluoromethyl-4,5-difuoro-1,3-dioxole (PDD) and tetrafluoroethylene (TFE), maleated S-EB-S block copolymer, polycarbonate, ethylene vinyl alcohol copolymer, and the like. Still, other (II) polymers include homopolymers which can be utilized in minor amounts; these include: polystyrene, polydimethylsiloxane, polyolefins such as polybutylene, polyethylene, polyethylene copolymers, polypropylene, and the like. Polyurethane elastomers based on saturated hydrocarbon diols (Handlin, D., Chin. S., and Masse. M., et al. "POLYURETHANE ELASTOMERS BASED ON NEW SATURATED HYDROCARBON DIOLS" Published Society of Plastics Industry, Polyurethane Division, Las Vegas, Oct. 23, 1996) are also suitable for use in blending with the block copolymers (I) used in forming the crystal gels of the invention. Such saturated hydrocarbon diols include hydroxyl terminated oligomers of poly(ethylene-butylene) (EB), poly(ethylene-propylene) (EP), -E-EB-, -E-EP-, -B-EP-, -B-EB-, -E-EP-E-, -E-EB-B-, -B-EP-B-, -B-EB-B-, -E-B-EB-, -E-B-EP-, -EB-EP-, -E-EB-EP-, -E-EP-EB-, -B-EB-EP-, -B-EP-EB-, -E-EP-E-EP-, -E-EP-E-EB-, -B-EP-B-EP-, -B-EB-B-EB-, -B-EB-B-EP-, -E-EB-B-EP-, -E-EP-B-EB- and the like. As an example, thermoplastic polyurethane made with isocyanates and chain extenders such as TMPD and BEPD from saturated hydrocarbon diol KLP L-2203 having a hard segment contents of 22% exhibits clean phase separation of the hard and soft segments with glass a transition of -50° C. KLP L-2203 based TPU's can be mixed with the crystalline block copolymers to form soft crystal gels within the gel rigidity ranges of the invention. High butylene content SEBS block copolymers include Shell high molecular weight GRP6917 having a rubber Tg of about -38° C. to about -22° C., preferably -27° C., Toluene Viscosity at 10% solids at 25° C. of about 40 cp to about 120 cp, preferably about 70 cp and styrene content of about 20 to about 40, preferably about 33, tensile strength, psi of about 4000, elongation at break of about 600%.
Suitable polyolefins include polyethylene and polyethylene copolymers such as Dow Chemical Company's Dowlex 3010, 2021D, 2038, 2042A, 2049, 2049A, 2071, 2077, 2244A, 2267A; Dow Affinity ethylene alpha-olefin resin PL-1840, SE-1400, SM-1300; more suitably: Dow Elite 5100, 5110, 5200, 5400, Primacor 141--XT, 1430, 1420, 1320, 3330, 3150, 2912, 3340, 3460; Dow Attane (ultra low density ethylene-octene-1 copolymers) 4803, 4801, 4602,
The conventional term "major" means about 51 weight percent and higher (e.g. 55%, 60%, 65%, 70%, 75%, 80% and the like) and the term "minor" means 49 weight percent and lower (e.g. 2%, 5%, 10%, 15%, 20%, 25% and the like).
Example of (II) polymers, copolymers, and blends include: (a) Kraton G 1651, G 1654X; (b) Kraton G 4600; (c) Kraton G 4609; other suitable high viscosity polymer and oils include: (d) Tuftec H 1051; (e) Tuftec H 1041; (f) Tuftec H 1052; (g) Kuraray SEPS 4033; (h) Kuraray S-EB-S 8006; (i) Kuraray SEPS 2005; (j) Kuraray SEPS 2006 , and (k) blends (polyblends) of (a)-(h) with other polymers and copolymers include: (1) S-EB-S/SBS; (2) S-EB-S/SIS; (3) S-EB-S/(SEP); (4) S-EB-S/(SEB)n ; (5) S-EB-S/(SEB)n ; (6) S-EB-S/(SEP)n ; (7) S-EB-S/(SI).sub. n; (8) S-EB-S/(SI) multiarm; (9) S-EB-S/(SEB)n ; (10) (SEB)n star-shaped copolymer; (11) s made from blends of (a)-(k) with other homopolymers include: (12) S-EB-S/polystyrene; (13) S-EB-S/polybutylene; (14) S-EB-S/polyethylene; (14) S-EB-S/polypropylene; (16) SEP/S-EB-S, (17) SEP/SEPS, (18) SEP/SEPS/SEB, (19), SEPS/S-EB-S/SEP, (20), SEB/S-EB-S (21), EB-EP/S-EB-S (22), S-EB-S/EB (23), S-EB-S/EP (24), (25) (SEB)n s, (26) (SEP)n, (27) Kuraray 2007 (SEPS), (28) Kuraray 2002, (SEPS), (29) Kuraray 4055 (S-EB-EP-S) (30) Kuraray 4077 (S-EB-EP-S) (31) Kuraray 4045 (S-EB-EP-S) (32) (S-EB-EP)n, (33) (SEB)n, (34) EPDM, (35) EPR, (36) EVA, (37) coPP, (38) EMA, (39) EEA, (40) DuPont Teflon AF amorphous fluoropolymers, (41) Dow polydimethylsiloxane, (42) maleated S-EB-S (maleation level 2-30%), (43) (EP)n, (44) Kraton GRP6918 and the like.
Representative examples of commercial elastomers that can be combined with the block copolymers (I) described above include: Shell Kratons D1101, D1102, D1107, D1111, D1112, D1113X, D1114X, D1116, D1117, D1118X, D1122X, D1125X, D1133X, D1135X, D1184, D1188X, D1300X, D1320X, D4122, D4141, D4158, D4240, G1650, G1652, G1657, G1701X, G1702X, G1726X, G175OX, G1765X, FG19O1X, FG1921X, D2103, D2109, D2122X, D3202, D3204, 33226, D5298, D5999X, D7340, G1650, G1651, G1652, G4609, G4600, G1654X, G2701, G2703, G2705, G1706, G2721X, G7155, G7430, G7450, G7523X, G7528X, G7680, G7705, G7702X, G7720, G7722X, G7820, G7821X, G7827, G7890X, G7940, G1730M, FG19OlX and FG1921X. Kuraray's SEP, SEPS, S-EB-S, S-EB-EP-S Nos. 1001, 1050, 2027, 2003, 2006, 2007, 2008, 2023, 2043, 2063, 2050, 2103, 2104, 2105, 4033, 4045, 4055, 4077, 8004, 8006, 8007 and the like.
The amorphous S-EB-S and (S-EB)n (II) copolymers can have a broad range of styrene to ethylene-butylene ratios (S:EB) of about 20:80 or less to about 40:60 or higher. The S:EB weight ratios can range from lower than about 20:80 to above about 40:60 and higher.
The Brookfield Viscosity of a 5 weight percent solids solution in toluene at 30° C. of 2006, 4045, 4055, 4077 typically range about 20-35, about 25-150, about 60-150, about 200-400 respectively. Typical Brookfield Viscosities of a 10 weight percent solids solution in toluene at 30° C. of 1001, 1050, 2007, 2063, 2043, 4033, 2005, 2006, are about 70, 70, 17, 29, 32, 50, 1200, and 1220 respectively. Typical Brookfield Viscosity of a 25 weight percent solids solution in toluene at 25° C. of Kraton D1101, D1116, D1184, D1300X, G1701X, G1702X are about 4000, 9000, 20000, 6000, 50000 and 50000 cps respectively. Typical Brookfield Viscosity of a 10 weight percent solids solution in toluene at 25° C. of G1654X is about 370 cps.
Suitable block copolymers (II) and their typical viscosities are further described. Shell Technical Bulletin SC:1393-92 gives solution viscosity as measured with a Brookfield model RVT viscometer at 25° C. for Kraton G 1654X at 10% weight in toluene of approximately 400 cps and at 15% weight in toluene of approximately 5,600 cps. Shell publication SC:68-79 gives solution viscosity at 25° C. for Kraton G 1651 at 20 weight percent in toluene of approximately 2,000 cps. When measured at 5 weight percent solution in toluene at 30° C., the solution viscosity of Kraton G 1651 is about 40. Examples of high viscosity S-EB-S triblock copolymers includes Kuraray's S-EB-S 8006 which exhibits a solution viscosity at 5 weight percent at 30° C. of about 51 cps. Kuraray's 2006 SEPS polymer exhibits a viscosity at 20 weight percent solution in toluene at 30° C. of about 78,000 cps, at 5 weight percent of about 27 cps, at 10 weight percent of about 1220 cps, and at 20 weight percent 78,000 cps. Kuraray SEPS 2005 polymer exhibits a viscosity at 0.5 weight percent solution in toluene at 30° C. of about 28 cps, at 10 weight percent of about 1200 cps, and at 20 weight percent 76,000 cps. Other grades of S-EB-S, SEPS, (SEB)n (SEP)n polymers can also be utilized in the present invention provided such polymers exhibits the required high viscosity. Such S-EB-S polymers include (high viscosity) Kraton G 1855X which has a Specific Gravity of 0.92, Brookfield Viscosity of a 25 weight percent solids solution in toluene at 25° C. of about 40,000 cps or about 8,000 to about 20,000 cps at a 20 weight percent solids solution in toluene at 25° C..
The styrene to ethylene and butylene (S:EB) weight ratios for the Shell designated polymers can have a low range of 20:80 or less. Although the typical ratio values for Kraton G 1651, 4600, and 4609 are approximately about 33:67 and for Kraton G 1855X approximately about 27:73, Kraton G 1654X (a lower molecular weight version of Kraton G 1651 with somewhat lower physical properties such as lower solution and melt viscosity) is approximately about 31:69, these ratios can vary broadly from the typical product specification values. In the case of Kuraray's S-EB-S polymer 8006 the S:EB weight ratio is about 35:65. In the case of Kuraray's 2005 (SEPS), and 2006 (SEPS), the S:EP weight ratios are 20:80 and 35:65 respectively. The styrene to ethylene-ethylene/propylene (S:EB-EP) ratios of Kuraray's SEPTON 4045, 4055, and 4077 are typically about 37.6, 30, 30 respectively. More typically the (S:EB-EP) and (S:EP) ratios can vary broadly much like S:EB ratios of S-EB-S and (SEB)n from less than 19:81 to higher than 51:49 (as recited above) are possible. It should be noted that multiblock copolymers including SEPTON 4045, 4055, 4077 and the like are described in my cited copending parent applications and are the subject matter of related inventions.
The block copolymers (II) such as Kraton G 1654X having ratios of 31:69 or higher can be used and do exhibit about the same physical properties in many respects to Kraton G 1651 while Kraton G 1654X with ratios below 31:69 may also be use, but they are less advantageous due to their decrease in the desirable properties of the final gel.
Plasticizers (III) particularly advantageous for use in practicing the present invention are will known in the art, they include rubber processing oils such as paraffinic and naphthenic petroleum oils, highly refined aromatic-free paraffinic and naphthenic food and technical grade white petroleum mineral oils, and synthetic liquid oligomers of polybutene, polypropene, polyterpene, etc. The synthetic series process oils are high viscosity oligomers which are permanently fluid liquid nonolefins, isoparaffins or paraffins of moderate to high molecular weight.
The amount of plasticizing oil (III) sufficient to achieve gel rigidities of from less than about 2 gram Bloom to about 1,800 gram Bloom range from less than about 250 to about 3,000 parts by weight of a plasticizing oil.
Examples of representative commercially available plasticizing oils include Amoco® polybutenes, hydrogenated polybutenes, polybutenes with epoxide functionality at one end of the polybutene polymer, liquid poly(ethylene/butylene), liquid hetero-telechelic polymers of poly(ethylene/butylene/styrene) with epoxidized polyisoprene and poly(ethylene/butylene) with epoxidized polyisoprene: Example of such polybutenes include: L-14 (320 Mn), L-50 (420 Mn), L-100 (460 Mn), H-15 (560 Mn), H-25 (610 Mn), H-35 (660 Mn), H-SO (750 Mn), H-100 (920 Mn), H-300 (1290 Mn), L-14E (27-37 cst @100° F. Viscosity), H-300E (635-690 cst @210° F. Viscosity), Actipol E6 (365 Mn), E16 (973 Mn), E23 (1433 Mn), Kraton L-2203 and Kraton L-1203, EKP-206, EKP-207, HPVM-2203 and the like. Example of various commercially oils include: ARCO Prime (55, 70, 90, 200, 350, 400 and the like), Duraprime and Tufflo oils (6006, 6016, 6016M, 6026, 6036, 6056, 6206, etc) , other white mineral oils include: Bayol, Bernol, American, Blandol, Drakeol, Ervol, Gloria, Kaydol, Litetek, Lyondell (Duraprime 55, 70, 90, 200, 350, 400, etc), Marcol, Parol, Peneteck, Primol, Protol, Sontex, Witco brand white oils including RR-654-P and the like. Generally, plasticizing oils with average molecular weights less than about 200 and greater than about 700 may also be used (e.g., H-300 (1290 Mn)).
Comparisons of oil extended S-EB-S triblock copolymers have been described in Shell Chemical Company Technical Bulletin SC:1102-89 (April 1989) "KRATON® THERMOPLASTIC RUBBERS IN OIL GELS" which is incorporated herein by reference.
The crystal gels forming the floss can be made non-adhearing, non-sticking, (non-tacky), by incorporating an advantage amount of stearic acid (octadecanoic acid), metal stearates (e.g., calcium stearate, magnesium stearate, zinc stearate, etc.), polyethylene glycol distearate, polypropylene glycol ester or fatty acid, and polytetramethylene oxide glycol disterate, waxes, stearic acid and waxes, metal stearate and waxes, metal stearate and stearic acid. The use of stearic acid alone do not reduce tack. The amount of stearic acid is also important. As an example, ratio of 200 grams stearic acid to 2,000 gram of S-EB-S (a ratio of 0.1) will result in spotted tack reduction on the surface of the gel. A ratio of 250 to 2,000 will result in spotted crystallized stearic acid regions on the surface of the gel or spotted tack reduction. A ratio of 300 to 2,000 will result in complete tack reduction with large stearic acid crystallized regions on the surface of the gel. When microcrystalline waxes are incorporated together with stearic acid, the crystallization of stearic acid completely disappears from the surface of the gel. For example excellent result is achieved with 200 grams of stearic acid, 150 grams of microcrystalline wax and 2,000 grams of S-EB-S. The same excellent result is achieved when S-EB-S is adjusted to 3,000 grams, 4,000 grams, etc. The same result is achieved with (I) copolymers as well as in combination with polymers (II) such as SEPS, S-EB-EP-S, (S-EB-EP)n, (SEB)n, (SEP)n polymers. Moreover, when about 50 grams of tetrakistmethylene 3-(3'5'di-tertbutyl-4"-hydroxyphenyl) propionate) methane is use as a tack reducing blooming agent, tack is completely removed from the surface of the gel after two to three weeks of blooming.
The crystal gels forming the floss can also contain useful amounts of conventionally employed additives such as stabilizers, antioxidants, antiblocking agents, colorants, fragrances, flame retardants, flavors, other polymers in minor amounts and the like to an extend not affecting or substantially decreasing the desired properties. Additives useful in the crystal gel of the present invention include: tetrakis(methylene 3-(3',5'-di-tert-butyl-4"-hydroxyphenyl) propionate) methane, octadecyl 3-(3",5"-di-tertbutyl-4"-hydroxyphenyl) propionate, distearyl-pentaerythritol-diproprionate, thiodiethylene bis-(3,5-ter-butyl-4-hydroxy) hydrocinnamate, (1,3,5-trimethyl-2,4,6-tris[3,5-di-tert-butyl-4-hydroxybenzyl] benzene), 4,4"-methylenebis(2,6-di-tert-butylphenol), steraric acid, oleic acid, stearamide, behenamide, oleamide, erucamide, N,N"-ethylenebisstearamide, N,N"-ethylenebisoleamide, sterryl erucamide, erucyl erucamide, oleyl palmitamide, stearyl stearamide, erucyl stearamide, calcium sterate, other metal sterates, waxes (e.g., polyethylene, polypropylene, microcrystalline, carnauba, paraffin, montan, candelilla, beeswax, ozokerite, ceresine, and the like), teflon (TFE, PTFE, PEA, FEP, etc), polysiloxane, etc. The crystal gel can also contain metallic pigments (aluminum and brass flakes), TiO2, mica, fluorescent dyes and pigments, phosphorescent pigments, aluminatrihydrate, antimony oxide, iron oxides (Fe3 O4, --Fe2 O3, etc.), iron cobalt oxides, chromium dioxide, iron, barium ferrite, strontium ferrite and other magnetic particle materials, molybdenum, silicones, silicone fluids, lake pigments, aluminates, ceramic pigments, ironblues, ultramarines, phthalocynines, azo pigments, carbon blacks, silicon dioxide, silica, clay, feldspar, glass microspheres, polymer microspheres, barium ferrite, wollastonite and the like. The report of the committee on Magnetic Materials, Publication NMAB-426, National Academy Press (1985) is incorporated herein by reference.
The crystal gels denoted as "G" can be physically interlocked with a selected material denoted as "M" to form composites as denoted for simplicity by their combinations Gn Mn, Gn Mn Gn l Mn Gn Mn, Mn Gn Gn, Gn Gn Mn, Mn Mn Mn Gn, Mn Mn Mn Gn Mn, Mn Gn Gn Mn, Gn Mn Gn Gn, Gn Mn Mn Gn, Gn Mn Mn Gn, Gn Gn Mn Mn, Gn Gn Mn Gn Mn, Gn Mn Gn Gn, Gn Gn Mn, Gn Mn Gn Mn Mn, Mn Gn Mn Gn Mn Gn, Gn Gn Mn Mn Gn, Gn Gn Mn Gn Mn Gn, and the like or any of their permutations of one or more Gn with Mn and the like, wherein when n is a subscript of M, n is the same or different selected from the group consisting of foam, plastic, fabric, metal, concrete, wood, glass, ceramics, synthetic resin, synthetic fibers or refractory materials and the like; wherein when n is a subscript of G, n denotes the same or a different gel rigidity of from about 2 gram to about 1,800 gram Bloom). The gels of the composites can be formed in combination with a selected amount of at least one polymer or copolymer selected from the group consisting of poly(styrene-butadiene-styrene), poly(styrene-butadiene), poly(styrene-isoprene-styrene), poly(styrene-isoprene), poly(styrene-ethylene-propylene), low viscosity poly(styrene-ethylene-propylene-styrene), low viscosity poly(styrene-ethylene-butylene-styrene), poly(styrene-ethylene-butylene), polystyrene, polybutylene, poly(ethylene-propylene), poly(ethylene-butylene), polyproplyene, or polyethylene, wherein said selected copolymer is a linear, branched, multiarm, or star shaped copolymer are useful as dental floss.
The crystal gels forming the floss are prepared by blending together the components including other additatives as desired at about 23° C. to about 100° C. forming a paste like mixture and further heating said mixture uniformly to about 150° C. to about 200° C. until a homogeneous molten blend is obtained. Lower and higher temperatures can also be utilized depending on the viscosity of the oils and amounts of multiblock copolymers (I) and polymer (II) used. These components blend easily in the melt and a heated vessel equipped with a stirrer is all that is required. Small batches can be easily blended in a test tube using a glass stirring rod for mixing. While conventional large vessels with pressure and/or vacuum means can be utilized in forming large batches of the instant crystal gels in amounts of about 40 lbs or less to 10,000 lbs or more. For example, in a large vessel, inert gases can be employed for removing the composition from a closed vessel at the end of mixing and a partial vacuum can be applied to remove any entrapped bubbles. Stirring rates utilized for large batches can range from about less than 10 rpm to about 40 rpm or higher.
The crystal gel articles can be formed by blending, injection molding, extruding, spinning, casting, dipping and other conventional methods. For example, Shapes having various cross-section can be extruded. The crystal gels can also be formed directly into articles or remelted in any suitable hot melt applicator and extruded into shaped articles and films or spun into threads, strips, bands, yarns, or other shapes. With respect to various shapes and yarn, its size are conventionally measured in denier (grams/9000 meter), tex (grams/1000 meter), and gage (1/2.54 cm). Gage, tex, denier can be converted as follows: tex=denier/9=specific gravity (2135/gage), for rectangular cross section, tex=specific gravity (5806×103) (th) (w)/9, where th is the thickness and w the width of the strip, both in centimeters. General descriptions of (1) block copolymers, (2) elastomeric fibers and conventional (3) gels are found in volume 2, starting at pp. 324-415, volume 6, pp 733-755, and volume 7, pp. 515 of ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING, 1987 which volumes are incorporated herein by reference.
Not only do the crystal gels forming the floss have all the desirable combination of physical and mechanical properties substantially similar to high viscosity amorphous S-EB-S gels such as high elongation at break of at least 1,600%, ultimate tensile strength of about 8×105 dyne/cm2 and higher, low elongation set at break of substantially not greater than about 2%, substantially about 100% snap back when extended to 1,200% elongation, and a gel rigidity of substantially from about 2 gram to about 1,800 gram Bloom and higher, the crystal gels of the present invention exhibit improved tear resistance and resistance to fatigue not obtainable from amorphous S-EB-S or S-EP-S gels at corresponding gel rigidities.
The crystal gels forming the floss of the present invention exhibit one or more of the following properties. These are: (1) tensile strength of about 8×105 dyne/cm2 to about 107 dyne/cm2 and greater; (2) elongation of less than about 1,600% to about 3,000% and higher; (3) elasticity modules of about 104 dyne/cm2 to about 106 dyne/cm2 and greater; (4) shear modules of about 104 dyne/cm2 to about 106 dyne/cm2 and greater as measured with a 1, 2, and 3 kilogram load at 23° C.; (5) gel rigidity of about less than about 2 gram Bloom to about 1,800 gram Bloom and higher as measured by the gram weight required to depress a gel a distance of 4 mm with a piston having a cross-sectional area of 1 square cm at 23° C.; (6) tear propagation resistance greater than the tear resistance of amorphous S-EB-S gels at corresponding gel rigidities; (7) resistance to fatigue greater than the fatigue resistance of amorphous S-EB-S gels at corresponding gel rigidities; (8) and substantially 100% snap back recovery when extended at a crosshead separation speed of 25 cm/minute to 1,200% at 23° C. Properties (1), (2), (3), and (6) above are measured at a crosshead separation speed of 25 cm/minute at 23° C.
The crystal gels can be formed in any shape; the original shape can be deformed into another shape (to contact a regular or regular surface) by pressure and upon removal of the applied pressure, the composition in the deformed shape will recover back to its original shape.
For purposes of dental flossing, while flossing between two closely adjacent teeth, especially between two adjacent teeth with substantial contact points and more especially between two adjacent teeth with substantial amalgam alloy metal contact points showing no gap between the teeth, it is critical that the crystal gel resist tearing, shearing, and crazing while being stretched to a high degree in such situations. For example, dental crystal gel floss can take the form of a disk where the segments of the circumference of the disk is stretched for flossing between the teeth. Other shaped articles suitable for flossing include threads, strips, yarns, tapes, etc., mentioned above.
In all cases, the tear strength of crystal gels are higher than that of amorphous gels. For example, the crystal gels made from high viscosity S-E-EB-S and S-E-EP-S copolymers are resistant to tearing when under high stress or shear than high viscosity typical S-EB-S and S-EP-S copolymer gels.
In order for gels to be useful as a dental floss, it must overcome the difficult barriers of high shearing and high tearing under extreme elongation and tension loads. The difficulties that the gels must overcome during flossing can be viewed as follows: during the action of flossing, the gel is stretched from no less than about 200% to about 1,100% or higher, the gel floss is deformed as it is pulled down with tearing action between the contacting surfaces of the teeth, then, the wedge of gel floss is sheared between the inner contacting surfaces of the teeth, and finally, the elongated wedged of gel floss is pulled upwards and out between the surfaces of the teeth. The forces encountered in the act of flossing are: tension, shearing, tearing under extreme tension.
This invention advances the flossing art by providing strong, soft, and extreme tear resistant gels made from multiblock copolymers which gels are substantially as soft as the gums surrounding the teeth.
Gel floss formed from the gels has many advantages over conventional dental floss such as regular and extra fine waxed and unwaxed nylon floss, spongy nylon fiber floss, and waxed and unwaxed expanded and unexpended teflon floss. Such conventional floss are not recommended for use by children, since a slip or sudden snap in forcing the floss between the teeth may cause injury to the gums which often times results in bleeding. For sensitive gums and inflamed gums which has become red and puffy, it is difficult to floss at, near, and below the gumline. The soft gel floss with softness substantially matching the softness of the gums are of great advantage for use by children and for flossing teeth surrounded by sensitive and tender gums.
The shear resistant characteristics of the gels can be indirectly determined by subjecting the gel to the shear forces of a pair of twisting strings and the resulting inward pulling forces of the twisting strings can be directly read off of a spring scale. As a pair of strings are gradually twisted, typical values will range from less than one pound to fifty pounds and greater. As the string is being twisted (simulating increased shearing forces), the measured pulling forces can range from a low value of 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 . . . to values of 40, 50, 60, 70, 80 pounds and greater.
Gel material of low strength can not resist the tremendous shearing action of the twisting strings. The twisting action of the strings can exhibit a first order twist, a second order twist, or higher order twists. A first order twist refers to one or more twists of a pair of strings (i.e., a pair of strings when twisted together forms a small tight binding helix). A second order twist refers to one or more large binding helixes build up by a pair of strings that have been twisted beyond the maximum number of twist which normally produce small tight binding helixes of the first order kind. Similarly, a third order twist refers to a much larger tightly binding helix build up by the maximum number of second order twists produced by the pair of twisting strings. The third order twist may be manifested by the appearance of a branch of two or more twist of the first order twisting strings.
The order of twisting will increase (from a one, two, three, and higher order twist) until the rubber band breaks. Likewise, a looped string with one end attached to a spring scale and the other end attached to a fixed anchor can be twisted into a first, second, third, and higher ordered twist state. This method can be utilized to directly measure the force generated for each ordered twist states. The static force generated by twisting a string on a spring scale is a way of determining the shear force generated in the shearing action of forcing the gel floss between two closely contacting teeth when flossing.
In considering dental flossing criteria, one or more of the following conditions can be regarded as critical factors for dental flossing gels.
SHEAR RESISTANT CRITERIA
For the gels to be considered useful for flossing, the gels, critically, should withstand a twisting string shearing force of at least about 5 Kg, more advantageously at least about 8 Kg, and still more advantageously at least about 10 Kg of inward pulling force of a pair of twisting strings measured directly on a spring scale.
FLOSSING CYCLE CRITERIA
For the gels to be considered useful for flossing, the gels, critically, should advantageously be able to perform at least 4 flossing cycles, more advantageously 8 cycles, and still more advantageously of about 20 cycles without breaking apart when a 3.0 mm diameter gel strand is tested on a set of simulated upper front teeth fully contacting under a uniform spring load of (0.9027 Kg) two pounds. The simulated upper front teeth comprises two small stainless steel rollers (3/8" dia.) facing lengthwise parallel and forced together so as to form a contact length of 1/2 inches under a spring load of two pounds as measured by a Entran® model ELO-200-4 load cell adjusted by a straight micrometer at room temperature.
GEL STRENGTH CRITERIA
For the gels to be considered useful for flossing, the gels, critically, should advantageously exhibit a tensile strength of at least 5 Kg/cm2 (when extended to break as measured at 180° U bend around a 5.0 mm mandrel attached to a spring scale) and more advantageously at least 8 Kg/cm2, and still more advantageously of about 10 Kg/cm2 and higher. The high and gels useful as dental floss can exhibit tensile strengths at break of at least 20 Kg/cm2, more advantageously of at least 40 Kg/cm2, and exceptionally more advantageously at least 60 Kg/cm2. Typically, the tensile strengths range from about 20 Kg/cm2 to about 110 Kg/cm2 and higher, more typically from about 30 Kg/cm2 to 80 Kg/cm2 and higher, especially more typically from about 40 Kg/cm2 to about 90 Kg/cm2 and higher, and exceptionally typically from about 50 Kg/cm2 to about 100 Kg/cm2 and higher.
PROPAGATING TEAR CRITERIA
As a minimum, for the Gels to be considered useful for flossing, the gels, critically, should advantageously exhibit a propagating tear force (when propagating a tear as measured at 180° U bend around a 5.0 mm diameter mandrel attached to a spring scale) of at least about 1 Kg/cm, more advantageously at least 2 Kg/cm, and still more advantageously of about 3 Kg/cm and higher. The gels useful as dental floss can exhibit tear strengths of at least 4 Kg/cm and higher, more advantageously of at least 6 Kg/cm and higher, exceptionally more advantageously of at least 8 Kg/cm and higher. Typically, the tear propagation strength can range from about 5 Kg/cm to about 20 Kg/cm and higher, more typically from about less than 5 Kg/cm to about 25 Kg/cm and higher, especially more typically form about less than 6 Kg/cm to about 30 Kg/cm and higher, and exceptionally more typically from about less than 8 Kg/cm to about 35 Kg/cm and higher.
For the Gels to be considered useful for flossing, the gels, critically, should advantageously exhibit a propagating tension tear force (when a cylindrical sample is notched and a tear is initiated at the notched area and propagated past its maximum cylindrical diameter by length-wise stretching of the cylindrical sample) of at least about 1 Kg/cm, more advantageously at least 2 Kg/cm, and still more advantageously of about 4 Kg/cm and higher. The extreme tear resistant gels typically will exhibit even higher tension tear values.
The rigidities of the extreme tear resistant useful for flossing can advantageously range from about 350 gram to about 1,800 gram Bloom, more advantageously from about 400 gram to about 1,500 gram Bloom, especially more advantageously from about 450 gram to about 1,200 gram Bloom, still more advantageously from about 450 gram to about 1,000 gram Bloom, and less advantageously at values of greater than 1,800 gram Bloom.
HIGH STRESS RUPTURE CRITERIA
This is demonstrated by forming very soft gel samples, for example 100 parts copolymer to 800 parts plasticizing oil. The soft gel is made in a 16 mm×150 mm test tube, the gel cylinder is cut or notched at one point about its cross-section and gripped lengthwise tightly in the left hand about this cross-section point and a length of exposed gel is gripped lengthwise around the adjacent cross-section point tightly by the right hand as close to the left hand as possible without stretching. With the two hands gripping the gel sample's cross-section about the notched point, the hands are moved in opposite directions to tear apart the gel sample at the cross-section point. The high shearing action by the gripping hands is done at the fastest speed possible as can be performed by human hands. Using this demonstration, the crystal gels will not easily break or tear completely apart, whereas, amorphous S-EB-S and S-EP-S gels break or tears apart easily. Likewise the various crystal gels of the invention described herein are tested and found to be more resistant to high stress rupture than typical SEBS and SEPS gels. For floss, the improved resistance high stress rupture is essential.
In general, as a minimum, the flossing gels should exhibit several critical properties, including advantageously the ability to:
(1) withstand a shearing force of at least about 5 Kg under the string twisting test described above,
(2) perform at least 4 flossing cycles without breaking apart when tested on a set of simulated upper front teeth fully contacting under a uniform spring load of two pound,
(3) exhibit a tensile strength of at least 5 Kg/cm2 and higher,
(4) exhibit a propagating tear force at 180° U bend tear test of at least about 1 Kg/cm, and
(5) exhibit a propagating tension tear force (on a notched cylindrical sample) of at least about 1 Kg/cm.
For use as a dental floss, the gel is made (by extruding, spinning, casting, etc) as a continuous gel strand, the gel strand can be in the shape of a fiber of a selected diameter (from less than about 0.15 to about 5.0 mm and greater) as a continuous tape having a selected width and thickness (less than 0.10 mm thin to about 5.0 mm and thicker) or in any desired shape suitable for flossing. The fiber, tape or a selected shape is then cut to a desired length, rolled up and placed into a dispenser suitable for containing and dispensing a measured use amount of gel floss. The continuous fiber and tape can be partly cut or notched for measured single or multiple use. When the floss is pulled from the dispenser to a point showing the notched or cut mark on the length of gel floss, the lid is pushed down on the gel floss nipping it and allowing the floss to be further pulled and separated at the notched or cut point. Additionally, a suitable floss dispenser containing a measured length of gel floss can be fitted with a cutting edge attached to its lid or on its body and the uncut and un-notched gel floss can be dispensed from the dispensing container and cut at the desired measured use length by pressing close the dispenser cutting edge down on the floss so as to nip and cut the gel or by simply closing the dispenser lid or running the gel along the cutting edge on the dispenser body separating a useful length of gel floss.
In practice, typically during flossing, a gel strand will under go various deformations, some of these deformations can be measured, including original shape, extended shape under tension, nipping force, and nipped deformation under a measured force and width. Typically, any shaped gel strand can be used for flossing, a square cross-section, a circular cross-section, a rectangular cross-section, round, oval, etc. For example, a 2.35 mm diameter strand when extended under a force of 2.5 kg can be nipped down to 0.14 mm thickness (along a 3 mm uniform width of its cross-section) by a force of 0.9072 Kg (2.0 pound force), a reduction of 16.78:1; a 1.89 mm diameter strand when extended under a force of 2.5 kg can be nipped down to 0.14 mm thickness by a force of 0.9072 Kg (2.0 pound force), a reduction of 13.5:1; a 2.75 mm diameter strand when extended under a force of 2.5 kg can be nipped down to 0.19 mm thickness by a force of 0.9072 Kg (2.0 pound force), a reduction of 14.4:1; and a 2.63 mm diameter strand when extended under a force of 2.5 kg can be nipped down to 0.19 mm thickness by a force of 0.9072 Kg (2.0 pound force), a reduction of 13.8:1, the cross-section of the gel floss can be reduced to any degree by stretching and nipping (from less than about 1% to about 1,600% and higher). Advantageously, a gel having the required strength, tear resistance, gel rigidity, and other characteristics described can be formed into a floss of any selected cross-section and thickness provided the floss is capable of being stretched when flossing under tension without breaking. Typically the stretching or pulling force is from about less than 0.1 Kg to about 3 Kg and higher. The cross-section of the strand of gel floss should be capable of being nipped by a 0.9027 Kg (2 pounds) force applied across a width of 3 mm from its original cross-sectional dimensions to a nipped thickness of about 3.0 mm to about 0.02 mm and lower, more advantageously from about 2.5 mm to about 0.04 mm and lower, still more advantageously from about 2.0 mm to about 0.08 mm and lower; especially advantageously from about 1.5 mm to about 0.15 mm and lower; especially more advantangeously from about 1.2 mm to about 0.20 mm and lower; especially still more advantageously from about 1.0 mm to about 0.25 mm and lower.
The gels made from higher viscosity copolymers (i) are resistant to breaking when sheared than triblock copolymer gels. This can be demonstrated by forming a very soft gel, for example 100 parts copolymer to 800 parts plasticizing oil. The soft gel is cut into a strip of 2.5 cm×2.5 cm cross-section, the gel strip is gripped lengthwise tightly in the left hand about its cross-section and an exposed part of the gel strip being gripped lengthwise around its cross-section tightly by the right hand as close to the left hand as possible without stretching. With the two hands gripping the gel strip's cross-section, the hands are moved in opposite directions to shear apart the gel strip at its cross-section. The shearing action by the gripping hands is done at the fastest speed possible as can be performed by human hands. The shearing action is performed at a fraction of a second, possible at about 0.5 seconds. Using this demonstration, the copolymer (I) gels will not easily break completely apart as would gels formed from triblock copolymers. In some cases, it will take two, three, or more attempts to shear a high viscosity copolymer (I) gel strip this way. Whereas, a lower viscosity triblock copolymer gel strip can be sheared apart on the first try. For gels made from copolymers with viscosities of 5 wt % solution in Toluene, their shear resistance will decrease with decreasing viscosity. For example, the shear strengths as tested by hand shearing described above of gels made from copolymers having viscosities of 150, 120, 110, 105, 95, 90, 89, 85, 70, 60, 58, 48, 42, 40, 35, 28, 27, 25, 21 cps, and the like can be expected to decrease with decreasing viscosity.
The tensile strengths of multiblock copolymer gels made from higher viscosity copolymers (I) can be slightly lower than or equal to the tensile strengths of gels made from lower solution viscosity triblock copolymers (II).
Strands of gels comprising higher viscosity multiblock copolymers will perform better than gel strands made from gels of lower viscosity triblock copolymers when used in flossing amalgam molars and more than three times better when used in flossing front teeth.
Gels, in general, will exhibit higher tensile and greater tear resistance than their parent gels containing higher concentrations of plasticizer.
As compared to spongy nylon, regular waxed nylon, and extra fine unwaxed nylon when flossing amalgam molars, the performance of multiblock copolymer gels are on the average substantially better.
While advantageous components and formulation ranges based on the desired properties of the multiblock copolymer gels nave been disclosed herein. Persons of skill in the art can extend these ranges using appropriate material according to the principles discussed herein. All such variations and deviations which rely on the teachings through which the present invention has advanced the art are considered to be within the spirit and scope of the present invention.
The invention is further illustrated by means of the following illustrative embodiments, which are given for purpose of illustration only and are not meant to limit the invention to the particular components and amounts disclosed.
Gels of 100 parts of high viscosity linear Kraton G1651 (amorphous S-EB-S), Septon 8006 (amorphous S-EB-S), Kraton GRP6918 (SEPS) and a high viscosity radial amorphous midblock segment (SEB)n triblock copolymers and 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 200 white oil (plasticizer) are melt blended and samples molded, the bulk gel rigidities are found to be within the range of 2 to 1,800 gram Bloom and the tensile strength, notched tear strength, and resistance to fatigue are found to decrease with increase amounts of plasticizers and unsuitable for use as floss.
Gels of 100 parts of high viscosity linear (S-EB-S), (S-EP-S), (S-B-EP-S), (S-B-EB-S) (S-B-EP-B-S), (S-B-EB-B-S), (S-B-EB-EP-S), (S-B-EP-EB-S), (S-EB-EP-S), and (S-EP-B-EP-S) block copolymers and 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 200 white oil (plasticizer) are each melt blended and samples molded, the bulk gel rigidities are found to be within the range of 2 to 1,800 gram Bloom and the tensile strength, notched tear strength, and resistance to fatigue are found to decrease with increase amounts of plasticizers and unsuitable for use as floss.
Gels of 100 parts of high viscosity linear (S-EB25 -EP-S), (S-E-EB25 -S) (S-EP-E-EP-S), (S-E-EB-S), (S-E-EP-S), (S-E-EP-E-S), (S-E-EB-B-S), (S-E-EB-E-S), (S-E-B-EB-S), (S-E-B-EP-S), (S-E-EB-EP-S), (S-E-EP-EB-S), (S-E-EP-E-EP-S), (S-E-EP-E-EB-S), (S-E-EB-B-EP-S), (S-E-EP-B-EB-S), (S-E-EP-E-EP-E-S), (SE-EP-E-EB-S), (S-E-EP-E-EP-EB-S), (S-E-EP-E-EP-E-S), and (S-E-EP-EB-EP-EB-B-S) block copolymers and 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 200 white oil (plasticizer) are each melt blended and samples molded, the bulk gel rigidities are found to be within the range of 2 to 1,800 gram Bloom and the tensile strength, notched tear strength, and resistance to fatigue and stress rupture are found to be greater than that of amorphous gels of Example II and suitable for use as floss.
Example III is repeated using plasticizers L-14, L-50, L-100, H-15, H-25, H-35, H-50, H-100, H-300, L-14E, H-300E, Actipol E6, E16, E23, Kraton L-1203, EKP-206, EKP-207, HPVM-2203, Amoco C-60, Piccolyte S10, Duraprime (55, 70, 90, 200, 350, 400), Tufflo (6006, 6016, 6016M, 6026, 6036, 6056, 6206) Bayol, Bernol, American, Blandol, Drakeol, Ervol, Gloria, and Kaydol, the bulk gel rigidities are found to be within the range of 2 gram to 1,800 gram Bloom and the tear resistance of the multiblock copolymers at corresponding rigidities are found to be substantially higher than the tear resistance of the triblock copolymer gels of EXAMPLES I or II.
Example III is repeated using plasticizers L-14, L-50, L-100, H-15, H-25, H-35, H-50, H-100, H-300, L-14E, H-300E, Actipol E6, E16, E23, Kraton L-1203, EKP-206, EKP-207, HPVM-2203, Amoco C-60, Piccolyte S10, Duraprime (55, 70, 90, 200, 350, 400), Tufflo (6006, 6016, 6016M, 6026, 6036, 6056, 6206,) Bayol, Bernol, American, Blandol, Drakeol, Ervol, Gloria, and Kaydol, the bulk gel rigidities are found to be within the range of 2 gram to 1,800 gram Bloom and the tear resistance of the multiblock copolymers at corresponding rigidities are found to be substantially higher than the tear resistance of the triblock copolymer gels of EXAMPLE I or II.
A gel composition of 100 parts of Kuraray's S-E-EP-S 4055 copolymer and 400 parts by weight of Duraprime 200 white oil was made following Example I and extruded and drawn (from a 7.15 mm diameter orifice) into a strand of uniform diameter onto a take-up roll of continuous lengths. The strand diameter was varied by increasing and decreasing the speed of the take-up roll. The continuous strand of varying diameter gel strand was cut to suitable lengths for use and testing as dental floss. Additional gel was also casted in varying thickness and tested. The results of samples tested are shown in Table 3, #4-7; Table 4, #12-15 and 20; Table 5 #22, 23, 27-29; Table 6 #36-32; Table 7, #40-43, #76 and 77. Sample Nos. 76 and 77 were tested together. Sample 77 exhibited higher tensile strength after 27.75% of plasticizing oil was extracted (with 2.89 parts by weight of oil remaining), its rigidity remained substantially unchanged.
A gel composition of 100 parts of Kraton G1651 and 400 parts by weight of Duraprime 200 white oil was made following Example I and extruded and drawn (from a 7.15 mm diameter orifice) into a strand of uniform diameter onto a take-up roll of continuous lengths. The strand diameter was varied by increasing and decreasing the speed of the take-up roll. The continuous strand of varying diameter gel strand was cut to suitable lengths for use and testing as dental floss. Additional gel was also casted in varying thickness and tested. The results of samples tested are shown in Table 3B, #8-11; Table 4, #16-19 and 21; Table 5, #24-26; Table 6, #33-35; and Table 7, #36-39.
TABLE 3A______________________________________Flossing Cycles to BreakSample cross-section 2 Floss amalgram 3 FlossNo. Floss Type size molars to fronts______________________________________1 4 Unwaxed 0.30 18 200+ spongy nylon2 5 Regular waxed 0.11 11 200+ nylon3 6 Extra fine 0.06 6 200+ unwaxed nylon______________________________________
TABLE 3B______________________________________Flossing Cycles to BreakSample Relaxed/extended 2 Floss amalgram 3 FlossNo. Floss Type dia. (mm) molars to break fronts to______________________________________4 7 Gel 2.42/0.16 37 765 7 Gel 2.63/0.17 29 836 7 Gel 2.75/0.17 36 1837 7 Gel 2.83/0.20 20 748 8 Gel 3.22/0.22 8 309 8 Gel 2.48/0.31 4 2010 8 Gel 3.16/0.33 6 4411 8 Gel 2.86/0.24 5 29______________________________________
1 floss dimension relaxed state and when extended during flossing cycles. 2 Test conditions: number of flossing cycles (before breaking) between amalgam alloy metal (fully contacting) lower, left first and second human back molars. 3 Test conditions: number of flossing cycles (before breaking) between upper human front teeth. 4 Oral-B Ultra Floss™, interlocking network of spongy nylon floss. 5 Johnson & Johnson regular waxed nylon floss. 6 Johnson & Johnson extra fine unwaxed nylon floss. 7 Gel made from 100 parts by weight of S-E-EP-S 4055 multiblock copolymer having a Brookfield viscosity of 90 as measured for a 5 wt % solution in toluene at 30° C. and 400 parts by weight of Duraprime 200 plasticizing oil. 8 Gel made from 100 parts by weight of SEBS Kraton G1651 copolymer having a Brookfield viscosity of 40 as measured for a 5 wt % solution in toluene at 30° C. 2,3 Any selected test methods may be utilized in testing the floss performance of the gels. For example, a set of simulated upper front teeth fully contacting under a uniform spring load of two pounds may be used in place of human teeth. Such simulated testing conditions may be more severe than conditions 2 and less severe than conditions 3 above.
TABLE 4______________________________________Tensile Strength of Gel StrandsSample Number of Radius Area Failure TensileNo. Strands (mm) (cm2) (Kg) (Kg/cm2)______________________________________12.sup. 3 1.325 0.165 9.00 54.5413.sup. 4 1.250 0.196 9.50 48.3914.sup. 4 1.421 0.253 9.50 37.4415.sup. 5 1.359 0.290 12.5 43.0816.sup. 2 2.14 0.287 14.0 48.7817.sup. 2 1.55 0.151 11.5 75.9518.sup. 2 1.17 0.086 8.50 98.8419.sup. 2 1.322 0.109 9.0 81.9620.sup. 6 1.375 0.356 14 39.3221.sup. 2 1.445 0.131 10 76.3376.sup. 1 1.22 0.0467 2.00 42.8277.sup.† 1 1.38 0.0598 4.00 66.88______________________________________ .sup.† Plasticizing oil extracted
TABLE 5______________________________________Tensilke Strength of Bulk Gels SamplesSample Cross-section Failure TensileNo. (cm2) (Kg) (Kg/cm2)______________________________________22 1.96 24.0 12.2423 1.56 25.0 16.0224 0.58 15.0 25.8325 0.602 16.0 26.5426 1.163 24.0 20.6427 0.913 21.0 23.0028 0.595 18.5 36.5629 0.702 19.0 27.06______________________________________
TABLE 6______________________________________180° U Bend Tear Propagation of Bulk Gels SamplesSample Tear width Failure Tear ForceNo. (cm) (Kg) (Kg/cm)______________________________________30 1.31 2.75 2.0931 1.28 3.0 2.3032 1.14 2.75 2.5633 1.53 2.75 1.7934 1.27 2.25 1.7635 1.26 2.25 1.77______________________________________
TABLE 7______________________________________Notched Gel Strand Tension Tear PropagationSample Strand Dia. Failure Tear ForceNo. (mm) (Kg) (Kg/cm)______________________________________36 2.86 0.75 2.6237 2.49 0.75 3.0138 3.09 0.60 1.9439 2.62 0.70 2.6740 2.54 0.60 2.3641 1.94 1.10 5.6742 1.58 0.75 4.7443 2.34 1.2 5.12______________________________________
The tensile strengths of gels made from higher viscosity copolymers are lower than the tensile strengths of gels made from lower solution viscosity copolymers. This was later found to be due to orientation effects and not considered significant.
The tear resistance of gels made from higher viscosity copolymers are higher than the tear resistance of gels made from lower solution viscosity copolymers.
Gel strands made from higher viscosity copolymers perform better than gel strands made of lower viscosity copolymers when used in flossing amalgam molars and more than three times better when used in flossing front teeth.
As compared to spongy nylon, regular waxed nylon, and extra fine unwaxed nylon when flossing amalgam molars, the performance of gels are on the average substantially better.
Examples below illustrate other modes of practice contemplated.
Gels of 100 parts of linear high content butylene (S-EB-S) and high content isopropylethyene (S-EP-S) block copolymers and 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 200 white oil (plasticizer) are each melt blended in admixture with the gels of Example III and samples molded, the bulk gel rigidities are found to be within the range of 2 to 1,800 gram Bloom and the tensile strength, notched tear strength, and resistance to fatigue and stress rupture are found to be greater than that of amorphous gels of Example II and suitable for use as floss.
The gels are especially advantageously useful when subjected to conditions of stretching, shearing, and tearing during flossing. The gels useful for flossing are characterized by low rigidities and high solution viscosity of the gels made from multiblock copolymers having two or more midblock polymer chains.
Tables 8-10 are illustrative in meeting one or more of the criteria detailed above.
__________________________________________________________________________8. Illustrative Modes of Practice Contemplatedfor multiblock copolymer Gels 5 Wt % Copolymer Number of100 Parts by Viscosity Sty- Parts by Wt floss cycles Samplewt (cps) rene % of Oil to break No.__________________________________________________________________________S-E-EP-S 90 30 300 30+ 44S-E-EP-E-S 60 30 300 30+ 45(S-E-EP)n 240 35 300 30+ 46(S-E-EP-E)n 240 35 300 30+ 47S-B-EP-S 90 30 300 30+ 48S-E-EB-S 90 35 300 30+ 49S-EB-EP-S 90 30 300 30+ 50S-E-EP-EP-S 90 30 300 30+ 51__________________________________________________________________________
TABLE 9__________________________________________________________________________Illustrative Modes of Practice Contemplatedfor multiblock copolymer Gels Wt % Copolymer Number Floss Viscosity Sty- Parts by Wt cycles to Sample100 Parts by wt (cps) rene % of Oil Break No.__________________________________________________________________________S-E-EP-EB-S 120 33 250 30+ 52S-E-EP-EP-S 120 33 250 30+ 53(S-B-EP)n 380 35 250 30+ 54(S-E-EB)n 380 35 250 30+ 55S-E-EP-E-EP-S 120 30 250 30+ 56S-E-EP-P-S 120 35 250 30+ 57S-E-B-EP-S 120 30 250 30+ 58S-E-EP-EP-E-S 120 30 250 30+ 59__________________________________________________________________________
TABLE 10__________________________________________________________________________Illustrative Modes of Practice Contemplatedfor multiblock copolymer (0.5-2.0 cmdiameters) Gel Strands 5 Wt % Copolymer Viscosity Styrene Parts by Wt # Floss cycles Sample100 Parts by wt (cps) % of Oil to Break No.__________________________________________________________________________S-E-EP-S 40 30 350 30+ 60S-E-EP-S 60 30 350 30+ 61(S-E-EP-EB)n 340 30 350 30+ 62(S-E-EP-EP-E)n 340 30 350 30+ 63S-E-EP-E-EP-E-S 90 30 350 30+ 64S-EB-EP-EP-S 90 35 350 30+ 65S-B-EB-B-S 90 30 350 30+ 66S-E-EP-EP-E-S 90 30 350 30+ 67__________________________________________________________________________
While certain features of this invention have been described in detail with respect to various embodiments thereof, it will, of course, be apparent that other modifications can be made within the spirit and scope of this invention, and it is not intended to limit the invention to the exact details shown above except insofar as they are defined in the following claims.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3660849 *||13 Jul 1970||9 May 1972||Minnesota Mining & Mfg||Deep submergence diving suit and insulative material therefor|
|US3821148 *||28 Sep 1973||28 Jun 1974||Exxon Research Engineering Co||Plasticized thermoplastic block copolymers|
|US3821149 *||28 Sep 1973||28 Jun 1974||Exxon Research Engineering Co||Plasticized thermoplastic semicrystalline block copolymers|
|US3827999 *||9 Nov 1973||6 Aug 1974||Shell Oil Co||Stable elastomeric polymer-oil compositions|
|US3860013 *||17 Jul 1972||14 Jan 1975||Czapor Henry P||Dental strip|
|US4136699 *||21 Jan 1977||30 Jan 1979||H. B. Fuller Company||Absorbent article with adhesive strip|
|US4151057 *||14 Aug 1978||24 Apr 1979||Shell Oil Company||High temperature adhesive made by exposure to radiation|
|US4176240 *||30 May 1978||27 Nov 1979||Bell Telephone Laboratories, Incorporated||Filled electrical cable|
|US4259540 *||20 Apr 1979||31 Mar 1981||Bell Telephone Laboratories, Incorporated||Filled cables|
|US4351913 *||4 Jan 1982||28 Sep 1982||Siecor Corporation||Filling materials for electrical and light waveguide communications cables|
|US4361508 *||20 Oct 1980||30 Nov 1982||Arco Polymers, Inc.||Cable filler compositions comprising a mixture of (a) styrene block copolymer, (b) crystalline polypropylene copolymer and (c) mineral oil|
|US4369284 *||28 Mar 1980||18 Jan 1983||Applied Elastomerics, Incorporated||Thermoplastic elastomer gelatinous compositions|
|US4432607 *||27 Oct 1981||21 Feb 1984||Bell Telephone Laboratories, Incorporated||Hot melt coated optical fiber|
|US4450849 *||27 Sep 1982||29 May 1984||Cerceo Chris A||Dental physio-tape|
|US4492428 *||16 Aug 1982||8 Jan 1985||At&T Bell Laboratories||Coated optical fiber|
|US4497538 *||10 Aug 1983||5 Feb 1985||Siecor Corporation||Filled transmission cable|
|US4509821 *||1 Sep 1983||9 Apr 1985||Sun Tech, Inc.||Filling material for electric cable|
|US4600261 *||12 Oct 1982||15 Jul 1986||Raychem Corporation||Apparatus and method for protection of electrical contacts|
|US4610738 *||4 Jan 1985||9 Sep 1986||Raychem Corporation||Encapsulating a splice with a gel-filled case|
|US4618213 *||18 Jan 1984||21 Oct 1986||Applied Elastomerics, Incorporated||Gelatinous elastomeric optical lens, light pipe, comprising a specific block copolymer and an oil plasticizer|
|US4643924 *||2 May 1985||17 Feb 1987||Raychem Corporation||Protective article comprising an elastic gel|
|US4662692 *||2 May 1985||5 May 1987||Raychem Corp.||Sealing member|
|US4678664 *||30 Sep 1982||7 Jul 1987||Basf Corporation||Mineral oil gels|
|US4680233 *||2 May 1985||14 Jul 1987||Raychem Corporation||Sealing material|
|US4690831 *||18 Jun 1986||1 Sep 1987||Raychem Corp.||Protective article|
|US4692369 *||9 Dec 1985||8 Sep 1987||Japan Gore-Tex, Inc.||Water-vapor-permeable, waterproof, highly elastic films|
|US4709982 *||13 Nov 1985||1 Dec 1987||Bicc Public Limited Company||Gelled oil filling compounds|
|US4716183 *||22 Nov 1985||29 Dec 1987||Raychem Corp.||Styrene-diene block copolymer compositions|
|US4721832 *||2 May 1986||26 Jan 1988||Raychem Corporation||Electrical connection sealing device|
|US4764535 *||6 Aug 1984||16 Aug 1988||Q'so, Inc.||Thermally applied sealants and process|
|US4798853 *||20 Jan 1987||17 Jan 1989||Shell Oil Company||Kraton G thermoplastic elastomer gel filling composition for cables|
|US4801346 *||30 Jul 1986||31 Jan 1989||The Kendall Company||Protective coatings|
|US4822834 *||19 Apr 1988||18 Apr 1989||The United States Of America As Represented By The Secretary Of The Air Force||Vibration damping composition suitable for outer space temperature variations|
|US4833193 *||14 Aug 1987||23 May 1989||Sieverding David L||Novel pressure sensitive adhesives|
|US4842931 *||19 Jul 1988||27 Jun 1989||Zook Gerald P||Affixable padding material using gelatinous viscoelastic polymer|
|US4864725 *||18 Apr 1988||12 Sep 1989||Raychem Corporation||Electrical connector and method of splicing wires|
|US4865905 *||9 Dec 1988||12 Sep 1989||Raychem Corporation||Article for protection of a substrate|
|US4880676 *||5 Apr 1988||14 Nov 1989||Raychem Corporation||Cable sealing apparatus|
|US4880878 *||29 Dec 1987||14 Nov 1989||Shell Oil Company||Block copolymer blends with improved oil absorption resistance|
|US4883431 *||26 Sep 1986||28 Nov 1989||Raychem Corporation||Gel-filled cap member|
|US4888070 *||1 Dec 1987||19 Dec 1989||Raychem Corporation||Environmental sealing of a substrate|
|US4889171 *||22 Jul 1987||26 Dec 1989||Minimo Ruben M||Foldable weather canopy for motor vehicles|
|US4889403 *||23 Dec 1987||26 Dec 1989||Raychem Corp.||Distribution optical fiber tap|
|US4900877 *||12 Jul 1988||13 Feb 1990||Raychem Corporation||Shielding and sealing gaskets|
|US4909756 *||31 Aug 1988||20 Mar 1990||Raychem Corp.||Splice case|
|US4929211 *||2 Dec 1988||29 May 1990||Softspot, Inc.||Hand held tactile toy|
|US4942270 *||12 Jul 1988||17 Jul 1990||Raychem Corporation||Cable sealing apparatus comprising heat resistant gel compositions|
|US4944363 *||6 Feb 1990||31 Jul 1990||Cap Toys, Inc.||Toy ball|
|US4944973 *||13 Sep 1989||31 Jul 1990||Raychem Corporation||Wraparound article|
|US4968747 *||30 Mar 1990||6 Nov 1990||Arco Chemical Technology, Inc.||Compatibilized blends of crystalline propylene polymers and styrenic copolymers|
|US4983008 *||1 Nov 1988||8 Jan 1991||Raychem Corporation||Strained distributed optical fiber communication system|
|US5026054 *||18 Jul 1990||25 Jun 1991||Cap Toys, Inc.||Toy|
|US5059748 *||26 Apr 1990||22 Oct 1991||Raychem Corporation||Cable splice enclosure|
|US5068138 *||23 Jul 1990||26 Nov 1991||Shell Oil Company||Elastomeric film|
|US5085597 *||28 Mar 1991||4 Feb 1992||Raychem Corporation||Corrosion protection apparatus|
|US5088734 *||9 Jan 1991||18 Feb 1992||Glava Gary L||Attenuating handle for recreational and work implements|
|US5098421 *||16 Oct 1989||24 Mar 1992||Zook Gerald P||Viscoelastic gel foot padding and medicating device|
|US5126182 *||22 Jan 1990||30 Jun 1992||Malden Mills Industries, Inc.||Drapable, water vapor permeable, wind and water resistant composite fabric and method of manufacturing same|
|US5149736 *||7 May 1990||22 Sep 1992||Raychem Corporation||Heat resistant gel compositions|
|US5153254 *||24 Jun 1988||6 Oct 1992||Applied Elastomerics, Inc.||Reusable lint remover|
|US5159022 *||21 May 1991||27 Oct 1992||Asahi Kasei Kogyo Kabushiki Kaisha||Crystalline block copolymer and process for producing the same|
|US5167649 *||17 Apr 1992||1 Dec 1992||Zook Gerald P||Drug delivery system for the removal of dermal lesions|
|US5173573 *||15 Mar 1991||22 Dec 1992||Raychem Corporation||Hermaphroditic gel closure|
|US5177143 *||27 Feb 1990||5 Jan 1993||Raychem Corporation||Method of making heat stable polymeric gelloid composition|
|US5181914 *||6 May 1992||26 Jan 1993||Zook Gerald P||Medicating device for nails and adjacent tissue|
|US5191752 *||4 May 1992||9 Mar 1993||Murphy Robert J||Elastomeric gel saddle|
|US5221534 *||4 Feb 1991||22 Jun 1993||Pennzoil Products Company||Health and beauty aid compositions|
|US5239723 *||24 Aug 1992||31 Aug 1993||Applied Elastomerics, Inc.||Gelatinous elastomer swabs|
|US5262468 *||23 May 1991||16 Nov 1993||Applied Elastomerics, Inc.||Thermoplastic elastomer gelatinous compositions|
|US5313019 *||2 Dec 1992||17 May 1994||N.V. Raychem S.A.||Closure assembly|
|US5324222 *||29 Apr 1992||28 Jun 1994||Applied Elastomerics, Inc.||Ultra-soft, ultra-elastic airfoils|
|US5330452 *||1 Jun 1993||19 Jul 1994||Zook Gerald P||Topical medicating device|
|US5334646 *||6 Oct 1992||2 Aug 1994||Applied Elastomerics, Inc.||Thermoplastic elastomer gelatinous articles|
|US5336708 *||24 Aug 1992||9 Aug 1994||Applied Elastomerics, Inc.||Gelatinous elastomer articles|
|US5459193 *||23 Feb 1995||17 Oct 1995||H. B. Fuller Licensing & Financing, Inc.||Polystyrene-ethylene/butylene-polystyrene hot melt adhesive|
|US5475890 *||30 Aug 1993||19 Dec 1995||Applied Elastomerics, Inc.||Gelatinous elastomer swabs|
|US5479952 *||23 Feb 1995||2 Jan 1996||Polteco, Inc.||Dental floss of ultra-high modulus line material with enhanced mechanical properties|
|US5508334 *||15 Nov 1993||16 Apr 1996||Applied Elastomerics, Inc.||Thermoplastic elastomer gelatinous compositions and articles|
|US5559165 *||8 Aug 1995||24 Sep 1996||National Starch And Chemical Investment Holding Corporation||Hot melt adhesives for bonding to sensitive areas of the human body|
|US5606149 *||13 Oct 1994||25 Feb 1997||Raychem Corporation||Closure for high voltage cable connections having an insulating gel to form gel to gel interface with other insulating gel|
|US5618882 *||10 May 1993||8 Apr 1997||Raychem Limited||Gels containing SEPS block polymers|
|US5624294 *||15 Nov 1993||29 Apr 1997||Applied Elastomerics, Inc.||Humdinger, gel spinner|
|US5626657 *||22 Aug 1996||6 May 1997||Teksource, Lc||Composite microsphere and lubricant mixture|
|US5633286 *||11 Aug 1994||27 May 1997||Applied Elastomerics, Inc.||Gelatinous elastomer articles|
|US5655947 *||21 May 1991||12 Aug 1997||Applied Elastomerics, Inc.||Ultra-soft, ultra-elastic gel airfoils|
|US5863977 *||12 Feb 1997||26 Jan 1999||H. B. Fuller Licensing & Financing, Inc.||High molecular weight S-EB-S hot melt adhesive|
|US5872201 *||6 Feb 1997||16 Feb 1999||The Dow Chemical Company||Interpolymers of ethylene, olefinic monomers, and aromatic vinylidene or hindered aliphatic or cycloaliphatic vinylidene monomers|
|US5929138 *||5 Nov 1996||27 Jul 1999||Raychem Corporation||Highly thermally conductive yet highly comformable alumina filled composition and method of making the same|
|US5952396 *||16 Jun 1997||14 Sep 1999||Raychem Corporation||Low modulus elastomer|
|US5994446 *||10 Jun 1996||30 Nov 1999||Raychem Limited||Gels made from triblock copolymers|
|US5994450 *||10 Jan 1997||30 Nov 1999||Teksource, Lc||Gelatinous elastomer and methods of making and using the same and articles made therefrom|
|WO1988000603A2 *||17 Jul 1987||28 Jan 1988||Raychem Limited||Gels comprising block copolymers|
|WO1990005166A1 *||9 Nov 1989||17 May 1990||Raychem Limited||Gels|
|WO1991005014A1 *||2 Oct 1990||18 Apr 1991||Raychem Limited||Gels|
|WO1993005113A1 *||7 Sep 1992||18 Mar 1993||Raychem Limited||Gels|
|WO1993023472A1 *||10 May 1993||25 Nov 1993||Raychem Limited||Gels|
|1||"SiloLiner" Sales literature from Knit-Rite medical (Mar. 1, 1999 three pages).|
|2||"Styrene-Diene Triblock Copolymers: Orientation Conditions and Mechanical Properties of the Oriented Materials" A. Weill and R. Pixa, Journal of Polymer Science Polymer Symposium 58, 381-394 (1977).|
|3||"Tuftec"--its characteristics and applications, Assahi Chemical.|
|4||Alizadeh, et al., "Effect of Topological Constraints on The Crystallization Behavior of Ethylene/allpha-Olefin Copolymers", PMSE, vol. 81, pp. 248-249, Aug. 22-26, 1999.|
|5||*||Alizadeh, et al., Effect of Topological Constraints on The Crystallization Behavior of Ethylene/allpha Olefin Copolymers , PMSE, vol. 81, pp. 248 249, Aug. 22 26, 1999.|
|6||*||ALPS South Corporation Gel Liners: NEW Easy Liner ELPX, ELDT and ELFR published fact sheet downloaded from the Internet on Aug. 10, 1999.|
|7||ALPS South Corporation-Gel Liners: NEW!Easy Liner ELPX, ELDT and ELFR published fact sheet downloaded from the Internet on Aug. 10, 1999.|
|8||*||Blends And Thermoplastic Interpenetrating Polymer Networks Of Polypropytlene And Polystyrene Block Poly(Ethylene Stat Butylene) Block Polytstyrene Triblock Copolymer. 1: Morphology And Structure Related Pproperties , Ohlesson, et al., Polymer Engineering and Science, Feb. 1996, vol. 36, No.4.|
|9||Blends And Thermoplastic Interpenetrating Polymer Networks Of Polypropytlene And Polystyrene-Block-Poly(Ethylene-Stat-Butylene)-Block-Polytstyrene Triblock Copolymer. 1: Morphology And Structure-Related Pproperties , Ohlesson, et al., Polymer Engineering and Science, Feb. 1996, vol. 36, No.4.|
|10||Chen, H., et al, "Classification of Ethylene-Styrene Interpolymers Based on Comonomer Content", J. Appl. Polym. Sci., 1998, 70, 109.|
|11||*||Chen, H., et al, Classification of Ethylene Styrene Interpolymers Based on Comonomer Content , J. Appl. Polym. Sci., 1998, 70, 109.|
|12||Chung P. Park and George P. Clingerman, "Compatibilization of Polyethylene-Polystyrene Blends with Ethylene-Styrene Random Copolymers", the Dow Chemical Company, May 1996.|
|13||*||Chung P. Park and George P. Clingerman, Compatibilization of Polyethylene Polystyrene Blends with Ethylene Styrene Random Copolymers , the Dow Chemical Company, May 1996.|
|14||*||D. C. Prevorsek, et al., Origins of Damage Tolerance in Ultrastrong Polyethylene Fibers and Composites:, Journal of Polymer Science: Polymer Symposia No. 75, 81 104 (1993).|
|15||D. C. Prevorsek, et al., Origins of Damage Tolerance in Ultrastrong Polyethylene Fibers and Composites:, Journal of Polymer Science: Polymer Symposia No. 75, 81-104 (1993).|
|16||Guest, et al., "Structre/Property Relationships of Semi-Crystalline Ethylene-Styrene Interpolymers (ESI)", PMSE, vol. 81, pp. 371-372, Aug. 22-26, 1999.|
|17||*||Guest, et al., Structre/Property Relationships of Semi Crystalline Ethylene Styrene Interpolymers (ESI) , PMSE, vol. 81, pp. 371 372, Aug. 22 26, 1999.|
|18||*||Kraton Polymers, May 1997, Shell Chemical Company.|
|19||*||Melt Miscibility In Blends Of Polypropylene, Polystryenhe Block Poly(Ethylene Sat Butylene) Block Polystyrene, and Processing Oil From Melting Point Depression , Ohlesson et al., Polymer Engineering and Science, 1996, vol. 36, No. 11.|
|20||Melt Miscibility In Blends Of Polypropylene, Polystryenhe-Block-Poly(Ethylene-Sat-Butylene)-Block-Polystyrene, and Processing Oil From Melting Point Depression, Ohlesson et al., Polymer Engineering and Science, 1996, vol. 36, No. 11.|
|21||*||Migration And Blooming Of Waxes To The Surface Of Rubber Vulcanizates , Nah, et al., J. Of Polymer Science: Polymer Physics Ed., vol. 18, 511 521 (1980).|
|22||Migration And Blooming Of Waxes To The Surface Of Rubber Vulcanizates, Nah, et al., J. Of Polymer Science: Polymer Physics Ed., vol. 18, 511-521 (1980).|
|23||*||SC:1102 89 Shell Chemical Technical Bulletin Kraton Thermoplastic Rubber in Oil Gels , Apr. 1989.|
|24||SC:1102-89 Shell Chemical Technical Bulletin "Kraton®Thermoplastic Rubber in Oil Gels", Apr. 1989.|
|25||*||Septon Trade Literature, Kuraray Co., Ltd. 1995.8 (4,000) 15 Pages.|
|26||*||Septon, High Performance Thermoplastic Rubber, Kurraray Co., Ltd., 1995.|
|27||*||Shell Chemical Co., Data Sheets: EKP 207 (093094 02) and L 1203 (SC:2384 950.|
|28||Shell Chemical Co., Data Sheets: EKP-207 (093094-02) and L-1203 (SC:2384-950.|
|29||*||Silipos manual, 1994.|
|30||*||Silipos product catlouge.|
|31||*||Silipos products catlouge sheets: Silosheath, Pressure Ulcers,Friction Sleeves with Gel, Gel E Rol & Friction Tape, Mesh Tubing,Silopad.|
|32||Silipos products catlouge sheets: Silosheath, Pressure Ulcers,Friction Sleeves with Gel, Gel-E-Rol & Friction Tape, Mesh Tubing,Silopad.|
|33||*||SiloLiner Sales literature from Knit Rite medical (Mar. 1, 1999 three pages).|
|34||Steve Hoenig, Bob Turley and Bill Van Volkenburgh, "Material Properties and Applications of Ethylene-Styrene Interpolymers", the Dow Chemical Company, Sep. 1996.|
|35||*||Steve Hoenig, Bob Turley and Bill Van Volkenburgh, Material Properties and Applications of Ethylene Styrene Interpolymers , the Dow Chemical Company, Sep. 1996.|
|36||*||Styrene Diene Triblock Copolymers: Orientation Conditions and Mechanical Properties of the Oriented Materials A. Weill and R. Pixa, Journal of Polymer Science Polymer Symposium 58, 381 394 (1977).|
|37||Teresa Plumley Karjaia, Y. Wilson Cheung and Martin J. Guest, "Melt Rheology and Processability of Ethylene/Styrene Interpolymers", the Dow Chemical Company, May 1997.|
|38||*||Teresa Plumley Karjaia, Y. Wilson Cheung and Martin J. Guest, Melt Rheology and Processability of Ethylene/Styrene Interpolymers , the Dow Chemical Company, May 1997.|
|39||*||Tuftec its characteristics and applications, Assahi Chemical.|
|40||*||Tuftec Trade Literature, Asani Chemical Co., Ltd., Synthetic Rubber Division, English and Japanese 14 Pages.|
|41||Y. Wilson Cheung and Martin J. Guest, "Structure, Thermal Transitions and Mechanical Properties of Ethylene/Styrene Copolymers", the Dow Chemical Company, May 1996. (17).|
|42||*||Y. Wilson Cheung and Martin J. Guest, Structure, Thermal Transitions and Mechanical Properties of Ethylene/Styrene Copolymers , the Dow Chemical Company, May 1996. (17).|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US6340027 *||16 Aug 1999||22 Jan 2002||Athena Nordic Ab||Extensible polishing mono-filament dental floss|
|US6545077||23 Aug 2001||8 Apr 2003||International Tape Partners, Llc||Monofilament dental tapes with substantive coatings|
|US6575176||23 Aug 2001||10 Jun 2003||International Tape Partners, Llc||Monofilament dental tapes with soft abrasive coatings|
|US6591844||23 Aug 2001||15 Jul 2003||Peri-Deat Limited||Elastomeric monofilament dental tapes|
|US6604534||23 Aug 2001||12 Aug 2003||International Tape Partners, Llc||Physical improvements in coated monofilament dental tapes|
|US6609527||23 Aug 2001||26 Aug 2003||International Tape Partners, Llc||Non-crystalline saliva-soluble coatings for elastomeric monofilament dental tapes|
|US6835015||11 Feb 2003||28 Dec 2004||Edizone, Lc||Jelly pens|
|US6884309||23 Aug 2001||26 Apr 2005||International Tape Partners Llc||Coated monofilament tape bobbins and methods for winding|
|US6905431||11 Feb 2003||14 Jun 2005||Edizone, Lc||Color changing balls and toys|
|US6907889||3 Jul 2003||21 Jun 2005||International Tape Partners, Llc||Non-crystalline saliva-soluble coatings for elastomeric monofilament dental tapes|
|US6916880||7 Apr 2003||12 Jul 2005||International Tape Partners, Llc||Monofilament dental tapes with substantive coatings|
|US7017591||30 Dec 2002||28 Mar 2006||International Tape Partners Llc||Particulate coated monofilament devices|
|US7025986||11 Feb 2002||11 Apr 2006||International Tape Partners Llc||Micromesh interproximal devices|
|US7101247||11 Feb 2003||5 Sep 2006||Edizone, Lc||Jelly blocks and jelly letters|
|US7134236 *||20 Jul 2002||14 Nov 2006||Applied Elastomerics, Inc.||Gelatinous elastomer compositions and articles for use as fishing bait|
|US7138079||11 Feb 2003||21 Nov 2006||Edizone, Lc||Methods for making foamed elastomer gels|
|US7148283 *||22 Jan 2003||12 Dec 2006||Hutchinson||Thermoplastic elastomer thin-walled film, method for preparing same and uses thereof|
|US7193002||21 Apr 2003||20 Mar 2007||Applied Elastomerics, Inc.||Adherent gels, composites, and articles|
|US7281541||16 Jun 2004||16 Oct 2007||Lorch Leonard G||Dental floss|
|US7678462||11 Jul 2005||16 Mar 2010||Honeywell International, Inc.||Spin-on-glass anti-reflective coatings for photolithography|
|US8342193||18 Mar 2005||1 Jan 2013||Wai-Kuen Lui||Flexible dental floss applicator and interdental gum stimulator|
|US8344088||15 Nov 2001||1 Jan 2013||Honeywell International Inc.||Spin-on anti-reflective coatings for photolithography|
|US8381742||24 Jan 2011||26 Feb 2013||Leonard G. Lorch||Dental floss|
|US8557877||8 Jun 2010||15 Oct 2013||Honeywell International Inc.||Anti-reflective coatings for optically transparent substrates|
|US8642246||14 Aug 2007||4 Feb 2014||Honeywell International Inc.||Compositions, coatings and films for tri-layer patterning applications and methods of preparation thereof|
|US8726917 *||4 Oct 2011||20 May 2014||W. L. Gore & Associates, Inc.||Stretch floss band|
|US8784985||11 Sep 2013||22 Jul 2014||Honeywell International Inc.||Anti-reflective coatings for optically transparent substrates|
|US8863762||5 Nov 2010||21 Oct 2014||Colgate-Palmolive Company||Elastomeric dental floss|
|US8864898||31 May 2011||21 Oct 2014||Honeywell International Inc.||Coating formulations for optical elements|
|US8967161||5 Nov 2010||3 Mar 2015||Colgate-Palmolive Company||Elastomeric dental floss|
|US8992806||25 Aug 2011||31 Mar 2015||Honeywell International Inc.||Antireflective coatings for via fill and photolithography applications and methods of preparation thereof|
|US9069133||12 Nov 2002||30 Jun 2015||Honeywell International Inc.||Anti-reflective coating for photolithography and methods of preparation thereof|
|US20020145066 *||23 Aug 2001||10 Oct 2002||Michael Schweigert||Coated monofilament tape bobbins and methods for winding|
|US20030168077 *||30 Dec 2002||11 Sep 2003||Brown Dale G.||Coated micromesh dental devices overcoated with imbedded particulate|
|US20030178044 *||11 Feb 2002||25 Sep 2003||Brown Dale G.||Micromesh interproximal devices|
|US20030200983 *||30 Dec 2002||30 Oct 2003||Brown Dale G.||Particulate coated monofilament devices|
|US20030225196 *||7 Apr 2003||4 Dec 2003||International Tape Partners, Llc||Monofilament dental tapes with substantive coatings|
|US20030232177 *||11 Feb 2003||18 Dec 2003||Edizone, Lc||Jelly pen holder|
|US20030234462 *||11 Feb 2003||25 Dec 2003||Edizone, Lc||Method for making gel including salt reduction step|
|US20030235453 *||11 Feb 2003||25 Dec 2003||Pearce Tony M.||Jelly pens|
|US20030235662 *||11 Feb 2003||25 Dec 2003||Edizone, Lc||Color changing balls and toys|
|US20030236313 *||11 Feb 2003||25 Dec 2003||Edizone, Lc||Methods for making foamed elastomer gels|
|US20040048018 *||11 Feb 2003||11 Mar 2004||Pearce Tony M.||Firm balls and toys with slow rebound characteristics|
|US20040094181 *||3 Jul 2003||20 May 2004||Brown Dale G.||Non-crystalline saliva-soluble coatings for elastomeric monofilament dental tapes|
|US20050175551 *||24 Oct 2003||11 Aug 2005||Heng Cai||Silicon modified polyamide material useful for oral care|
|US20050199334 *||1 Apr 2005||15 Sep 2005||Michael Schweigert||Coated monofilament tape bobbins and methods for winding|
|US20050226820 *||10 Jun 2005||13 Oct 2005||Brown Dale G||Non-crystalline saliva-soluble coatings for elastomeric monofilament dental tapes|
|US20050228116 *||22 Jan 2003||13 Oct 2005||Hutchinson||Thermoplastic elastomer thin-walled film, method for preparing same and uses thereof|
|US20050279378 *||16 Jun 2004||22 Dec 2005||Lorch Leonard G||Dental floss|
|US20060084353 *||18 Oct 2004||20 Apr 2006||Wong Tak K||Reversible ball having hyper-elastic properties|
|US20060084354 *||29 Sep 2005||20 Apr 2006||Wong Tak K||Reversible ball having hyper-elastic properties and safety perforations|
|US20060112968 *||13 Jan 2006||1 Jun 2006||Brown Dale G||Particulate coated monofilament devices|
|US20060243297 *||29 Apr 2005||2 Nov 2006||Brown Dale G||Coated monofilament oriented HDPE dental tapes|
|US20060283477 *||16 Jun 2005||21 Dec 2006||Bryan Oronsky||Interdental cleaning article with functional messages|
|US20070107747 *||16 Oct 2006||17 May 2007||Whitehill Oral Technologies, Inc.||Cleaning perception oral care products|
|US20070157946 *||18 Mar 2005||12 Jul 2007||Wai-Kuen Lui||Flexible dental floss applicator and interdental gum stimulator|
|US20070181144 *||16 Oct 2006||9 Aug 2007||Whitehill Oral Technologies, Inc.||Coated dental devices with dry-to-the-touch, flavor-absorbing, saliva soluble coatings and methods for manufacturing|
|US20080113315 *||5 Oct 2007||15 May 2008||Danville Materials, Inc.||Elastic dental device|
|US20130081648 *||4 Oct 2011||4 Apr 2013||John W. Dolan||Stretch Floss Band|
|US20150265383 *||18 Mar 2015||24 Sep 2015||Flexi Floss Ltd.||Dental flossing device|
|CN102740796A *||5 Nov 2010||17 Oct 2012||高露洁-棕榄公司||Elastomeric dental floss|
|CN103327929A *||5 Nov 2010||25 Sep 2013||高露洁-棕榄公司||Elastomeric dental floss|
|CN103327929B *||5 Nov 2010||13 Apr 2016||高露洁-棕榄公司||弹性体牙线|
|WO2003066729A2 *||22 Jan 2003||14 Aug 2003||Hutchinson||Thermoplastic elastomer thin-walled film, method for preparing same and uses thereof|
|WO2003066729A3 *||22 Jan 2003||11 Mar 2004||Pierre Hoerner||Thermoplastic elastomer thin-walled film, method for preparing same and uses thereof|
|WO2006043990A2 *||3 Jun 2005||27 Apr 2006||Tak Ko Wong||Reversible ball having hyper-elastic properties|
|WO2006043990A3 *||3 Jun 2005||27 Sep 2007||Tak Ko Wong||Reversible ball having hyper-elastic properties|
|WO2011057095A1||5 Nov 2010||12 May 2011||Colgate-Palmolive Company||Elastomeric dental floss|
|WO2012060843A1||5 Nov 2010||10 May 2012||Colgate-Palmolive Company||Elastomeric dental floss|
|U.S. Classification||132/321, 132/329, 132/323|
|International Classification||A63H33/18, C08L51/00, C08L53/02, C08L53/00, A61C15/00, A61C15/04|
|Cooperative Classification||C08L53/025, C08L53/00, A61C15/00, C08L53/02, A63H33/185, A61C15/041, C08L51/00|
|European Classification||C08L53/02, C08L51/00, C08L53/02B, A61C15/00, A61C15/04B, A63H33/18W, C08L53/00|
|3 Feb 1999||AS||Assignment|
Owner name: APPLIED ELASTOMERICS, INC., CALIFORNIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CHEN, JOHN YOUNGFU;REEL/FRAME:010057/0466
Effective date: 19990203
Owner name: APPLIED ELASTOMERICS, INC., CALIFORNIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CHEN, JOHN YOUNGFU;REEL/FRAME:010129/0967
Effective date: 19990203
Owner name: APPLIED ELASTOMERICS, INC., CALIFORNIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CHEN, JOHN Y.;REEL/FRAME:010129/0949
Effective date: 19990203
|21 Jun 2004||FPAY||Fee payment|
Year of fee payment: 4
|30 Jun 2008||REMI||Maintenance fee reminder mailed|
|19 Dec 2008||LAPS||Lapse for failure to pay maintenance fees|
|10 Feb 2009||FP||Expired due to failure to pay maintenance fee|
Effective date: 20081219